Journal of Petroleum Science and Engineering 61 (2008) 1–8

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Journal of Petroleum Science and Engineering

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p e t r o l

Research paper

Psychrometric charts for water vapour in natural gas

David C. Shallcross ⁎
Department of Chemical and Biomolecular Engineering, University of Melbourne, Melbourne, Victoria 3010, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Psychrometric charts present in a graphical form physical property data for gas systems involving one or more
Received 25 April 2007 non-condensing gas components and a single condensing vapour component. Originally limited to studying
Accepted 19 October 2007 the humid air system of water vapour in dry air, the theory behind preparing psychrometric charts for water
vapour in natural gas is presented. To illustrate the technique two charts are prepared for a system in which
Keywords: the natural gas is 80.0 mol% methane, 15.0 mol% ethane and 5.0 mol% propane. One chart is prepared for the
natural gas temperature range of 0 to 60 °C at a system pressure of 101.3 kPa and the other chart for the range of 40 to
humidity
110 °C at a system pressure of 400.0 kPa. The charts are based upon semi-theoretical equations and make use
psychrometric chart
of published physical property data and correlations. The behaviour of the gas mixture is characterized by the
virial equation
virial equation of state truncated at the third term. The charts are constructed with the dry bulb temperature
and absolute humidity scales as the orthogonal axes. Curves of constant adiabatic saturation temperature,
constant relative humidity, constant gas specific volume and constant enthalpy deviation are plotted on the
charts. Using the theory presented psychrometric charts for any temperature range, system pressure and
natural gas composition may be prepared.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction 2. Modelling system behaviour

An understanding of the conditions under which water vapour
may condense from natural gas is important in the design and
operation of any system involving the use, transportation or storage of
natural gas. Even in this age of computer-aided design and physical
property databases, engineers still find it useful to have physical
property data presented graphically. Using a simple straight line or
curve overlaid onto a chart of physical property data variations in the
properties may be observed as a function of some changing parameter.
Psychrometric charts present in a graphical form physical property
data for gas systems involving one or more non-condensing gas
components and a single condensing vapour component. Originally
limited to studying the humid air system of water vapour in dry air,
psychrometric charts have now been extended to other systems
(Shallcross and Low, 1994; Shallcross 2005).
In this paper the application of psychrometric charts is extended to
consider systems involving water vapour in natural gas. The wide
range of natural gas compositions is represented in this study by
considering a three-component natural gas mixture of 80.0 mol% CH4,
15.0 mol% C2H6 and 5.0 mol% C3H8. However, nothing in the devel-
opment or application of the equations presented here limits the
system to just three non-condensing components. Two psychrometric
charts covering differing temperature ranges and differing pressures
are prepared to illustrate the preparation of such charts.
In modeling the system properties the gas phase is not assumed to
behave ideally. The effects of the dissolved gases and the pressure on
the properties of the condensed phase (i.e., the water) are accounted
for as is the effect of intermolecular forces on the properties of the
moisture. The virial equation of state truncated at the third term is
used to characterize the non-ideal behaviour. This method is chosen
from the many equations of state in the literature as virial coefficient
data is readily available for a range of systems and components. The
virial equation of state truncated at the third term is:
PT V̂ Bm Cm
¼1þ þ 2 ð1Þ
RT V̂ V̂
where, PT is the total pressure, V̂ is the molar volume of the gas
mixture, R is the gas constant, T is the absolute temperature, and Bm
and Cm are the second and third virial coefficients of the humid
natural gas, respectively.
In the development of the model equations which follow we shall
assume that the natural gas may be represented as a single com-
ponent, G. The vapour component (i.e., the water vapour) that readily
condenses will be denoted as V.
If xG is the mole fraction of the non-condensing natural gas, and xV
is the mole fraction of the water vapour then for a binary system:

Bm ¼ x2G BGG þ 2 xG xV BGV þ x2V BVV ð2Þ

⁎ Tel.: +61 3 8344 6614; fax: +61 3 8344 4153.

E-mail address: dcshal@unimelb.edu.au. Cm ¼ x3G CGGG þ 3 x3G xV CGGV þ 3 xG x2V CGVV þ x3V CVVV : ð3Þ

0920-4105/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.petrol.2007.10.002
2 D.C. Shallcross / Journal of Petroleum Science and Engineering 61 (2008) 1–8

Here Bii is the second virial coefficient of pure component i, BGV is repeated until the values for f and xGs no longer change significantly
the second virial interaction (or cross) coefficient for the binary between successive calculations.
system, Ciii is the third virial coefficient of pure component i, and, The absolute humidity at saturation, Hs, is the mass of the vapour
CGGV and CGVV are the third virial interaction parameters. component V per mass of component G. It may be expressed in terms of
A gas is saturated with a vapour when the partial pressure of the the mole fractions of the two components in the gas phase at saturation:
vapour is equal to its vapour pressure at the particular temperature.
For an ideal system we could write an expression relating the mole xVs MWV
Hs ¼ ð9Þ
fraction of the condensing vapour component at saturation, V, to its xGs MWG
vapour pressure:
where MWi is the molecular weight of component i.
PV The psychrometric charts are constructed with temperature plotted
xVs ¼ ð4Þ
PT on the x-axis and absolute humidity on the orthogonal y-axis. The
saturation line that describes the boundary of the psychrometric chart is
and drawn by plotting the absolute humidity at saturation, Hs, as a function
of temperature for a specified total pressure.
PT  PV The relative humidity, ϕ, is defined as the ratio of the mole fraction
xGs ¼ ð5Þ
PT of the vapour component, xV, in a given sample of the two-component
mixture to the mole fraction, xVs, in a sample of the mixture which is
where, xVs and xGs are the mole fractions of components V and G saturated with the vapour component at that temperature. Thus,
respectively at saturation, and PV is the vapour pressure of component
xV
V. However, since the system is not ideal an enhancement factor is /¼ : ð10Þ
xVs
used to account for the non-idealities in the system. Eq. (4) becomes,
In order to construct the curves of constant relative humidity an
f PV expression is required which relates the absolute humidity to the
xVs ¼ : ð6Þ
PT relative humidity, temperature and total pressure. It may be shown
that (Shallcross and Low, 1994):
A similar expression may be written for the non-condensing gas
component G: Hs /ð1  f PV =PT Þ
H¼ : ð11Þ
1  /f PV =PT
PT  f PV
xGs ¼ : ð7Þ
PT To construct the constant relative humidity curves, the system
pressure, PT, is first specified. Then for a given value of ϕ, the variables
The enhancement factor accounts for the effects of the dissolved f, Hs and PV are calculated for varying temperatures. These values are
gases and pressure on the properties of the condensed phase, and the then used in Eq. (11) to calculate the absolute humidity as a function of
effect of intermolecular forces on the properties of the moisture itself. temperature. When plotted this data yields the constant relative
The enhancement factor may be written in terms of the virial co- humidity curves.
efficients and the other properties of the system (Hyland and Wexler, The specific volume of a humid mixture, ν, is defined as the volume
1983): of the mixture per unit mass of the dry gas:
"
#
ð1 þ jPV ÞðPT  PV Þ  12 j PT2  PV2 V̂
ln f ¼ V̂ Vc þlnð1  kH xGs PT Þ m¼ : ð12Þ
RT xG MWG
2x3Gs ð2  3xGs ÞPT2 x2 PT 2x2 PT
 2
BGG BGV þ Gs BGG  Gs BGV Applying this definition and using Eq. (1) curves of constant spe-
ðRT Þ RT RT
  cific volume may be plotted for a given system pressure.
PT  PV  x2Gs PT x2Gs ð1  3xGs Þð1  xGs ÞPT2
 BGG  BGG BVV The wet bulb temperature is usually considered as the temperature
RT ðRT Þ2 measured by a cylindrical thermometer, the outside surface of which
2 2
6x ð1  xGs Þ PT
2
2x ð1  xGs Þð1  3xGs ÞPT2 2
2
is kept wet with the liquid of the condensing component V, in this case
þ Gs 2
BVV BGV  Gs BGV
" ðRT Þ # ðRT Þ2 water. As the moist gas passes the thermometer some of the water
P 2  ð1 þ 3xGs Þð1  xGs Þ3 PT2 2 3x4 P 2 evaporates resulting in a cooling effect that causes the temperature of
 V BVV  Gs T2 B2GG
2ðRT Þ2
2ðRT Þ the wet bulb thermometer to drop. The drier the gas, the greater the
3x2Gs ð1 þ 2xGs ÞPT2 3x2Gs ð1  xGs ÞPT2 wet bulb depression. As the wet bulb temperature is a function of not
þ CGGV  CGVV only the dry bulb temperature and absolute humidity, but also such
" 2ðRT Þ2 #ðRT Þ
2
factors as the gas velocity past the thermometer, the diameter of
ð1 þ 2xGs Þð1  xGs Þ2 PT2  PV2 x3 P 2
 2
CVVV þ Gs T2 CGGG : ð8Þ the thermometer and the extent of radiative heat transfer, it is not
2ðRT Þ ðRT Þ possible to predict the wet bulb temperatures with precision.
Consequently we choose to plot instead curves of constant adiabatic
Here κ is the isothermal compressibility of the condensing com- saturation temperature.
ponent (i.e. the water), V̂Vc is the molar volume of the condensed For the conventional air–water system the adiabatic saturation
component V (either as a liquid or a solid), and kH is the Henry's Law temperature, Tad, is defined as the temperature at which water (liquid
constant to account for the solubility of component G in the con- or solid), by evaporating into moist air at a given dry bulb temperature,
densed phase. For a given temperature and total pressure, PT, Eqs. (7) T, and absolute humidity, H, can bring air to saturation adiabatically at
and (8) may be solved iteratively for the enhancement factor, f, and the same temperature, Tad, while the pressure PT, is maintained
the mole fraction of component G at saturation, xGs. In practice this is constant (ASHRAE, 1989). The adiabatic saturation temperature is also
done by first setting f = 1. xGs is then calculated using Eq. (7) and then known as the thermodynamic wet bulb temperature.
this value is used in Eq. (8) to calculate an estimate for the enhance- For a given G–V system, it may be defined as the temperature at
ment factor, f. The value for xGs is then re-calculated. The cycle is then which component V, present as either a liquid or a solid, by
 D.C. Shallcross / Journal of Petroleum Science and Engineering 61 (2008) 1–8
Fig. 1. Psychrometric chart for the water vapour–natural gas system at 101.3 kPa.

3
 4
D.C. Shallcross / Journal of Petroleum Science and Engineering 61 (2008) 1–8
Fig. 2. Psychrometric chart for the water vapour–natural gas system at 400.0 kPa.
 D.C. Shallcross / Journal of Petroleum Science and Engineering 61 (2008) 1–8 5

evaporating into the moist gas mixture at a given dry bulb natural gas of representation composition. The natural gas is assumed
temperature, T, and absolute humidity, H, can bring that mixture to to be represented by a three-component mixture of 80.0 mol%
saturation adiabatically at the same temperature, Tad, while the methane, 15.0 mol% ethane and 5.0 mol% propane. Neither the theory
pressure, PT, is maintained constant. nor the equations presented here limit the natural gas to just three
The calculation and representation of the specific enthalpy of the components. The only limitation is on the availability of the relevant
gas mixture requires special attention. The specific of the two- physical property data. Charts are presented for the dry bulb tempera-
component gas mixture is calculated by summing the ideal gas state ture range of 0 to 60 °C at 101.3 kPa system pressure, and for the dry
enthalpy and the residual enthalpy: bulb temperature range of 40 to 110 °C at a system pressure of 400 kPa.
 Z T   Z T  The model equations and physical property data were coded into a
ĥ ¼ xG ĥoG þ CPG VdT þ xV ĥoV þ CPV VdT FORTRAN program for each system. This program generates a file
2 To To 3 containing a set of instructions in the Postscript graphics language.
   
dB 1 T dC 1 5 When sent to a Postscript laser printer the two psychrometric charts
4
þ RT T
m
 Bm þ
m
 Cm : ð13Þ
dT V̂ m 2 dT 2 presented in Figs. 1 and 2 are generated. If the charts are printed using
V̂ m
a resolution of 600 dpi (23.6 dots/mm) then the curves may be plotted
In this equation To is the enthalpy datum temperature, CPG and CPV to a precision of about 0.01 °C.
are the ideal gas heat capacity of the gas and vapour respectively, and, The layout of Fig. 1 is typical of the psychrometric chart produced
ĥoG and ĥoV are the enthalpy corrections for both components by the process. Dry bulb temperature is plotted on the x-axis with
necessary to ensure that the enthalpy, ĥ, is in fact zero at the enthalpy absolute humidity plotted on the y-axis. The relative humidity, spe-
datum condition. cific volume, adiabatic saturation temperature and enthalpy deviation
Because of the nature of the equations governing the construction curves are all plotted as functions of dry bulb temperature and
of the constant adiabatic saturation temperature curves, lines of absolute humidity. The layout of the chart is self-explanatory. The
constant gas mixture enthalpy will lie nearly parallel to the adiabatic enthalpy datum condition for the water is taken as liquid water at its
saturation temperature curves. Rather than plotting two sets of curves vapour pressure at 0.01 °C.
having nearly the same slope, which would result in a chart difficult to
read, the gas mixture enthalpy data is presented in a different form. An 4. Discussion
enthalpy deviation term, ĥdev, is defined as being the difference
between the true specific enthalpy of a gas mixture and the specific The position of the saturation curve and hence the shape of the
enthalpy of the gas saturated at its adiabatic saturation temperature: psychrometric chart is influenced by the magnitude of the variation in
the enhancement factor with temperature. Fig. 3 shows the variation
ĥdev ¼ ĥ  ĥS;as : ð14Þ in the enhancement factor with temperature for water vapour in the
representative natural gas mixture at six different pressures ranging
When curves of constant enthalpy deviation are plotted on the from 0.100 MPa to 1.000 MPa. The enhancement factor increases with
psychrometric chart then the true specific enthalpy of a gas mixture increasing and the enhancement factor typically lies in the range,
can be determined by adding the enthalpy deviation for the point on 1.00 b f b 1.04.
the chart representing the mixture, to the enthalpy of the gas satu- All the correlations used to predict physical property behaviour in
rated at its adiabatic saturation temperature. this work have been the subject of extensive experimental studies to
validate them. This current study simply takes these accepted cor-
3. Chart preparation and production relations and applies them to produce graphical representations of the
data in the form of the psychrometric charts. All correlations have been
Using the equations presented here as well as the physical property applied well within their limitations. This technique has been suc-
data in Appendix A psychrometric charts have been prepared for a cessfully employed in the past by Shallcross and Low (1994) to develop
charts for the water vapour in air system which agree extremely closely
with those published by ASHRAE (1989) for that system.

5. Concluding remarks

Using published physical property data and correlation, and equa-

tions presented here, two high-precision psychrometric charts have
been constructed for water vapour in a gas mixture of methane,
ethane and propane. These charts illustrate how the techniques pre-
sented here may be used to prepare psychrometric charts for water
vapour in natural gas of any composition, provided the required
physical property data is available.

Appendix A. Physical property data

The construction of the charts requires information on the physical

properties of both the water vapour and the non-condensing
hydrocarbon gas mixture. As the charts are only as reliable as the
data available the most accurate and consistent data sets have been
used from the literature.

A.1. Water vapour

For water vapour the molecular weight is taken as 18.015, the

Fig. 3. Enhancement factor as a function of dry bulb temperature at different pressures. critical temperature as 647.35 K, the critical pressure as 22.118 MPa,
6 D.C. Shallcross / Journal of Petroleum Science and Engineering 61 (2008) 1–8

the compressibility factor at the critical point as 0.261 and the acentric This correlation is based upon one for the density of water as a
factor as 0.348. function of temperature presented by Hyland and Wexler (1983). Over
The second virial coefficient for water vapour is taken as (Hyland the temperature range from 173.15 K to 273.16 K the same workers
and Wexler, 1983): give the molar volume of ice as:

B ¼ T 0:05820  0:012234e1734:29=T ðA:1Þ V̂ VC ¼ 19:276404  4:50266  104 T þ 6:9468  104 T 2 ðA:7Þ

where B is expressed in cm3/mol and T is expressed in Kelvin. where V̂Vc is the molar volume of ice is expressed in cm3/mol, and T is
The third virial coefficient for water vapour is presented by Hyland expressed in Kelvin.
and Wexler (1983) in its pressure series form. Expressing it in terms of Keenan et al. (1978) tabulates the latent heat of vapourization of
the volume series form it is: water. Regression of the data between 0 and 110 °C yields the
correlation:
h i
C ¼T 2 752:82  2:31788e3645:09=T þ 1:49755e3468:58=T  14:2446e1734:29=T 104
k ¼ 2501:40  2:37341t þ 0:000805207t 2  1:69018  105 t 3
ðA:2Þ þ 1:81383  108 t 4 ðA:8Þ
where, C is expressed in cm6/mol2 and T is expressed in Kelvin. where, λ is expressed in kJ/kg, and t is expressed in °C.
The vapour pressure of water over the temperature range from 0 °C McGowan (1980) tabulates the enthalpy of water data to seven
to 200 °C is taken as (Hyland and Wexler, 1983): significant figures. Non-linear regression of the data between 0 and
110 °C yields the correlation:
X
3
ln PV ¼ ci T i þ 6:5459673 ln T ðA:3Þ
i¼1 0:00115 þ 4:21965t þ 0:198652t 2  2:93514  106 t 3 þ 1:003624  107 t 4
hf ¼
1 þ 0:0476516t
where, PV is the vapour pressure expressed in Pa, T is the absolute ðA:9Þ
temperature in Kelvin, and
where, hf is expressed in kJ/kg, t is expressed in °C, and, the enthalpy
c1 ¼ 5:8002206  103 datum condition is taken as liquid at 0 °C.
c0 ¼ 1:3914993
c1 ¼ 4:8640239  102 A.2. Natural gas
c2 ¼ 4:1764768  105
c3 ¼ 1:4452093  107 : The natural gas used in this study is assumed to have a composition
of 80.00 mol% CH4, 15.00 mol% C2H6 and 5.00 mol% C3H8. The average
Kell (1975) gives the isothermal compressibility of saturated liquid
molecular weight is 19.549. The critical point data for the three gas
water over the temperature range from 0 to 150 °C as:
components are presented in Table 1.
0 1 Since some of the correlations that follow require single values of
P5
i
B ci t C TC, PC, V̂C, ZC and ω for air these must be calculated. Kay's rule is used
B C 11
j ¼ B i¼0 C  10 ðA:4Þ to calculate a pseudo-critical temperature T′C for air:
@1 þ c6 t A
X
T CV ¼ xi TCi ðA:10Þ
i
where, κ is expressed in 1 / Pa, t is expressed in °C and
summed over all components.
for 0-V t V100-C for 100- V t V150-C
For the pseudo-critical pressure, P′C , the recommendations of Reid
c0 ¼ 5:088496  10 c0 ¼ 5:0884917  10
et al. (1977) are followed:
c1 ¼ 6:163813  101 c1 ¼ 6:2590623  101
c2 ¼ 1:459187  103 c2 ¼ 1:3848668  103
P 
: R xi ZCi T CV
c3 ¼ 2:008438  105 c3 ¼ 2:1603427  105 P CV ¼ Pi : ðA:11Þ
c4 ¼ 5:847727  108 c4 ¼ 7:2087667  108 i xi V̂ Ci
c5 ¼ 4:104110  1010 c5 ¼ 4:6545054  1010
c6 ¼1:967348  102 c6 ¼1:9859983  102 The acentric factor for the natural gas is simply taken as
X
For ice the isothermal compressibility is (Hyland and Wexler, xV¼ xi xi : ðA:12Þ
1983): i

j ¼ ð8:875 þ 0:0165T Þ  1011 ðA:5Þ The pseudo-critical compressibility factor, Z′C, is calculated from

where, κ is expressed in 1 / Pa, and T is expressed in Kelvin. Z CV ¼ Z ð0Þ þ xVZ ð1Þ ðA:13Þ
The molar volume of water is taken as:
where Z (0) = 0.2901 and Z (1) = −0.0879 at the critical point (Lee and
61692:295 þ 291:8088T
V̂ VC ¼ ðA:6Þ Kesler, 1975).
P5
ci T i
i¼0

where V̂Vc is the molar volume of water is expressed in cm3/mol, and Table 1
Molecular weight, critical point and acentric factor data
c0 ¼ 2403:360201
c1 ¼ 1:40758895 Gas MW TC PC V̂ C ZC ω
(K) (MPa) (m3/kmol)
c2 ¼ 0:1068287657
:
c3 ¼ 2:914492351  104 Methane 16.043 190.56 4.599 0.0986 0.286 0.0115
c4 ¼ 3:73497936  106 Ethane 30.069 305.32 4.872 0.1455 0.279 0.0995
Propane 44.096 369.83 4.248 0.2000 0.276 0.1523
c5 ¼ 2:1203787  1010
 D.C. Shallcross / Journal of Petroleum Science and Engineering 61 (2008) 1–8 7

The pseudo-critical volume, V̂′C , is calculated from Table 3

Ideal gas specific heat capacity coefficients for Eq. (A.29)
Z CVRT CV
V̂ CV ¼ : ðA:14Þ Gas c1 × 10− 4 c2 × 10− 4 c3 × 10− 3 c4 × 10− 4 c5 × 10− 2
P CV
Methane 3.3298 7.9933 2.0869 4.1602 9.9196
Thus, for the natural gas mixture Ethane 4.0326 13.422 1.6555 7.3223 7.5287
Propane 5.1920 19.245 1.6265 11.680 7.2360

T CV ¼ 216:74 K P CV ¼ 4:630 MPa V̂ C ¼ 0:1118 m3 =kmol

Z CV ¼ 0:287 xV¼ 0:0317

While a correlation for a second virial coefficient of the natural gas acentric factor, and g1 and g2 are both functions of the reduced
mixture is not available, correlations for the three gas components are temperature:
presented by Rowley et al. (2001). These correlations are of the form:

c2 c3 c4 c5 0:02432 0:00313
B ¼ c1 þ þ þ þ ðA:15Þ g1 ¼ 0:01407 þ  ðA:22Þ
T T3 T8 T9 Tr2:8 Tr10:5
where B is expressed in cm3/mol and T is expressed in Kelvin. Values
0:01770 0:040 0:003 0:00228
for the five parameters for each of the three natural gas components g2 ¼ 0:02676 þ þ 3:0  6:0  : ðA:23Þ
Tr2:8 Tr Tr Tr10:5
are presented in Table 2.
The second virial coefficient of the natural gas mixture, BGG, is
given by: The third virial coefficient of the natural gas mixture, CGGG, is given
XX by:
BGG ¼ xi xj Bij : ðA:16Þ
i j XXX
CGGG ¼ xi xj xk Bij : ðA:24Þ
Here, Bii is the second virial coefficient of pure component i, Bij is i j k

the second virial cross-coefficient, and xi is the mole fraction of

component i. Pitzer (1990) recommends that the second virial cross- Here CGGG is the third virial coefficient of pure component i, and
coefficients be estimated using the empirical correlation: Cijk is a third virial cross-coefficient which is estimated using the
empirical correlation of Orbey and Vera (1983):
" #
c3 þ xij c4 c5 þ xij c6 c7 þ xij c8
Bij ¼ V̂ cij c1 þ xij c2 þ þ þ ðA:17Þ
1=3
Trij Tr2ij Tr6ij Cijk ¼ Cij Cik Cjk ðA:25Þ

where the critical properties Tcij, V̂cij and ωij are defined as: where
qffiffiffiffiffiffiffiffiffiffiffi
Tcij ¼ Tci Tcj ðA:18Þ !2
R Tcij

Cij ¼ g1 þ xij g2 : ðA:26Þ
0 1=3 1=3 13
Pcij
V̂ ci þ V̂ cj
V̂ cij ¼ @ A ðA:19Þ
2 Here the cross-critical temperature, Tcij, is defined in Eq. (A.18) and
the cross-critical pressure is defined as
xi þ xj
xij ¼ : ðA:20Þ
2 2 !1=3 33
  
Zci Zcj 1=3 Zci Zcj
In Eq. (A.17), Pcij ¼ 4 Zci þ Zcj Tcij 4 þ 5 : ðA:27Þ
P ci Pcj
c1 ¼ 0:442259 c2 ¼ 0:725650
c3 ¼ 0:980970 c4 ¼ 0:218714 In Eq. (A.26), g1 and g2 are both functions of Trij as defined in Eqs.
:
c5 ¼ 0:611142 c6 ¼ 1:24976
(A.22) and (A.23) respectively.
c7 ¼ 0:11515624 c8 ¼ 0:189187
The ideal gas heat capacity for each component of the natural gas is
Reliable correlations for the third virial coefficients for the three assumed to be related to temperature by an equation of the form
components of the natural gas mixture are not available so the gen- (Rowley et al., 2001):
eralized empirical correlation of Orbey and Vera (1983) is used to
estimate this property for each component:  2  2
c3 =T c5 =T
CP ¼ c1 þ c2 þ c4 ðA:28Þ
sinhðc3 =T Þ coshðc5 =T Þ
CPC2
¼ g1 þ x g2 ðA:21Þ
ðRT Þ2
where, CP is expressed in J/(kmol K) and T is expressed in Kelvin.
where, C is the third virial coefficient, PC is the critical pressure, TC is Values for the five parameters for each of the three components are
the critical temperature, R is the universal gas constant, ω is the presented in Table 3.

Table 2 Table 4
Second virial coefficient parameters for Eq. (A.15) Henry's Law coefficients for Eq. (A.30) for the gas components in water

Gas c1 c2 × 10− 4 c3 × 10− 8 c4 × 10− 18 c5 × 10− 20 Gas c1 c2 × 10− 4 c3

Methane 51.075 −2.5181 −2.5601 5.9777 −5.7697 Methane − 215.301 1.0447 29.7802
Ethane 80.950 −6.1710 −14.350 67.600 − 97.400 Ethane −250.812 1.2695 34.7413
Propane 112.70 −9.9200 −45.100 309.00 −705.00 Propane −283.828 1.4434 39.4740
8 D.C. Shallcross / Journal of Petroleum Science and Engineering 61 (2008) 1–8

When integrated an expression for the change in specific enthalpy References

between T1 and T2 may be derived:
D ĥ ¼ c1 ðT2  T1 Þ þ c2 c3 ½ coth ðc3 =T2 Þ  coth ðc3 =T1 Þ
þ c4 c5 ½ tanh ðc5 =T2 Þ  tanh ðc5 =T1 Þ:
The solubility of the gas component in the liquid is considered by
making use of Henry's Law constants, kH. Based upon the data and
regressions presented in the volumes of the Solubility Data Series,
(Hayduk, 1982; Hayduk, 1986; Kertes, 1987) Henry's Law constants
may be related to temperature through equations of the form:
1
kH ¼
:
exp c1 þ cT2 þ c3 lnðT Þ
For the solubility of the three alkanes in water the appropriate
coefficients are presented in Table 4.
A.3. Henry's Law constants
Henry's Law constant for a mixture may be calculated from the
composition of the gas and the values of the Henry's Law constants for
the individual components:
1 X xj
¼ ðA:31Þ
kNG–V
H j kHj–V
where kNG–V
H is the Henry's Law constant for the natural gas mixture in
liquid V, xj is the mole fraction of component j in the dry gas mixture
and kjH–V is the Henry's Law constant for gas component j in liquid V.
Thus, Henry's law constant for natural gas in water:
ASHRAE, 1989. ASHRAE Handbook — Fundamentals SI Edition, American Society of
Heating, Refrigerating and Air-Conditioning Engineers, Atlanta, USA.
Hayduk, W., 1982. Solubility data series – Volume 9 – Ethane. Pergamon Press, Oxford.
ðA:29Þ Hayduk, W., 1986. Solubility data series – Volume 24 – Propane. Pergamon Press,
Oxford.
Hyland, R.W., Wexler, A., 1983. Formulations for the thermodynamic properties of dry
air from 173.15 K to 473.15 K, and of saturated moist air from 173.15 K to 372.15 K at
pressure to 5 MPa. ASHRAE Trans. 89, 520–535.
Keenan, J.H., Keyes, F.G., Hill, P.G., Moore, J.G., 1978. Steam Tables Thermodynamic
Properties of Water Including Vapour, Liquid and Solid Phases. John Wiley and Sons,
New York.
Kell, G.S., 1975. Density, thermal expansivity, and compressibility of liquid water from 0°
to 150 °C: correlations and tables for atmospheric pressure and saturation reviewed
ðA:30Þ and expressed on 1968 temperature scale. J. Chem. Eng. Data 20, 97–105.
Kertes, A.S., 1987. Solubility data series – Volume 27/28 – Methane. Pergamon Press,
Oxford.
Lee, B.I., Kesler, M.G., 1975. A generalised thermodynamic correlation based on the
three-parameter corresponding states. AIChE J. 21, 510–527.
McGowan, J.C., 1980. Isothermal compressibility of liquids, In: Weast, R.C., Astle, M.J.
(Eds.), CRC Handbook of Chemistry and Physics, 60th ed. CRC Press, Boca Racon,
Florida. F-16 – F-20.
Orbey, H., Vera, J.H., 1983. Correlation for the third virial coefficient using Tc, Pc and w as
parameters. AIChE J. 29, 107–113.
Pitzer, K.S., 1990. Second virial coefficients for mixed gases of low polarity. Fluid Phase
Equilib. 59, 109–113.
Reid, R.C., Prausnitz, J.M., Sherwood, T.K., 1977. The properties of gases and liquids, 3rd
ed. McGraw-Hill Book Company, New York.
Rowley, R.L., Wilding, W.V., Oscarson, J.L., Yang, Y., Rowley, R.J., Daubert, T.E., Danner, R.P.,
2001. DIPPR data compilation of pure compound properties. AIChE, New York.
Shallcross, D.C., 2005. Preparation of psychrometric charts for water vapour in Martian
atmosphere. Int. J. Heat Mass Transfer 48 (9), 1785–1796.
Shallcross, D.C., Low, S.L., 1994. Construction of psychrometric charts for systems other
than water vapour in air. Chem. Eng. Res. Des. 72 (6), 763–776.

1 0:8000 0:1500 0:0500

¼ CH –V þ C H –V þ C H –V : ðA:32Þ
kNG–V
H kH 4 kH2 6 kH3 6