FIG.

23-14
Pseudo Liquid Density of Systems Containing Methane and Ethane

23-23
 FIG. 23-15 9. Correct the density at 60°F and pressure to the actual
Density Correction for Compressibility of temperature using Fig. 23-17. Add the correction to the
Hydrocarbon Liquids density from Step 8.
This procedure is not valid in the critical region. Mixtures
at temperatures greater than 150 °F that contain more than
60 mol% methane or more than 80 mol% CO2 are problem
areas. Outside the near-critical region, calculated densities
usually are within 5% of experimental data35 and errors are
rarely greater than 8%. The best accuracy occurs for mixtures
containing mostly C5+ with relatively small amounts of dis-
solved gaseous components (errors are usually less than 3%).
Note that densities of C2+, C3+, CO2+, or C4+ mixtures can be
calculated by this procedure at various temperatures and
pressures, and that the gaseous components need not be pre-
sent.
Example 23-3 — Fig. 23-16 illustrates the procedure outlined
above.
Wt of C3 + 44.836 lbm
Density of C3 + = =
Vol o f C3 + 1.0128 ft3

= 44.275 lbm/ft3
 100 (0.567) 
Wt % C2 in C2 + =   = 1.25%
 0.567 + 44.836
45.403 + 17.485
Density of CO2 + = = 45.75 lbm/ft3
(45.403/44.0) + 0.3427
Wt% of CH4 in Total = 100(3.352)/66.241 = 5.1%
Pseudo-density of mixture at 60°F and 14.7 psia from
Fig. 23-14 = 42.9 1bm/ft3
Pressure correction to 1760 psia from Fig. 23-15 = +0.7
Density at 60°F and 1760 psia = 42.9 + 0.7 = 43.6 lb/ft3
Temperature correction to 120 °F from Fig. 23-17 = -1.8
Density at 120 °F and 1760 psia = 43.6- 1.8 = 41.8 lb/ft3

FIG. 23-16
Calculation of Liquid Density of a Mixture at 120°F and 1760 psia

(1) (2) (3) (4)=(2)•(3) (5) (6)=(4)/(5)

Mole Molecular Density (60°F),
Component Weight, lb Volume, cu ft
Fraction Weight lb/cu ft
Methane 0.20896 16.043 3.352 – –
Carbon Dioxide 0.39730 44.010 17.485 51.016 0.3427
Ethane 0.01886 30.070 0.567 – –
Propane 0.02387 44.097 1.053 31.619 0.0333
n-Butane 0.03586 58.123 2.084 36.423 0.0572
n-Pentane 0.02447 72.150 1.766 39.360 0.0449
n-Hexane 0.01844 86.177 1.589 41.400 0.0384
n-Heptane 0.02983 100.204 2.989 42.920 0.0696
n-Octane 0.02995 114.231 3.421 44.090 0.0776
n-Decane 0.18208 142.285 25.907 45.790 0.5658
n-Tetradecane 0.03038 198.394 6.027 47.815 0.1260

23-24
 FIG. 23-17
Density Correction for Thermal Expansion of Hydrocarbon Liquids

250

200
600

550
Density at 60˚ F minus density at temperature, lb per cu ft

180 500

450
160
400

350
140
300
120 275
250
100 225
200
180
160
140
80 120
100
80
60˚ F
60
40

40 20
0
-20
20 -40
-60
0 -80
-100
-20
-40

Density at 60˚ F, lb per cu ft

23-25
 Density from EZ*THERMO version of SRK using Example 23-4 — Determine the mean average boiling point
Costald92 = 41.815 lb/ft3. (MeABP) and the molecular weight for a 56.8° API petroleum
fraction with the following ASTM distillation data.
Experimental density35 at 120°F and 1760
psia = 41.2 lb/ft3 % Over Temperature, °F
IBP 100
Error = (41.8 - 41.2)/41.2 = 0.015, or 1.5%
5 130
10 153
BOILING POINTS, CRITICAL 20 191
PROPERTIES, ACENTRIC FACTOR, 30 217
VAPOR PRESSURE 40 244
50 280
Boiling Points 60 319
Fig. 23-18 shows the interconversion between ASTM D-86 70 384
distillation 10% to 90% slope and the different boiling points 80 464
used to characterize fractions of crude oil to determine the 90 592
properties; VARP, WARP, CARP, MeARP, and MABP. On the
basis of ASTM D-86 distillation data, the volumetric average EP 640
boiling (VARP) point is:
IBP = initialboiling point EP = end po int
VARP = (t10 + t30 + t50 + t70 + t90)/5 Eq 23-12

where the subscripts 10, 30, 50, 70, and 90 refer to the volume
percent recovered during the distillation. The 10% to 90%
slope used as the abscissa in Fig. 23-18 is:
slope = (t90- t10)/(90 -10) Eq 23-13
To use the graph, locate the curve for the distillation VARP in
the appropriate set for the type of boiling point desired. For
the known 10-90% slope, read a correction for the VABP from
the selected VABP curve.
Slope = (592 − 153)/80 = 5.49
VABP = (153 + 217 + 280 + 384 + 592)/5 = 325°F
Refer to Fig. 23-18. Read down from a slope of 5.49 to the
interpolated curve to 325 °F in the set drawn with dashed lines
(MeABP). Read a correction value of –54 on the ordinate.
Then
MeABP = 325 – 54 = 271°F

FIG. 23-18
Characterizing Boiling Points of Petroleum Fractions (From API Technical Data Book)

23-26
 The significance of the various average boiling points, inter-
conversion of D-86 and D-1160 A8TM distillations, and the
calculation of true-boiling point and atmospheric flash curves
from A8TM distillation data are in Chapters 3 and 4 of the API
Technical Data Book.36
Molecular weight can be calculated from Eq 23-14 using Me-
ABP in °R and S (specific gravity at 60°F):
MW = 204.38 (T0.118)(S1.88) e(0.00218T - 3.075 S) Eq 23-14
This relationship is valid in the molecular weight range of
70 to 720; the MeABP range of 97 to 1040 °F; and the API range
of 14° to 93°. The average error is about 7%. Eq. 23-14 works
best for molecular weights above 115; it tends to over-predict
below this value.
Example 23-5 — Calculation of molecular weight.
From Example 23-4:
S = 0.7515 for 56.8° API
MeABP = 271 + 460 = 731°R
Using Eq 23-14,
MW = 204.38(731)0.118 (0.7515)1.88 e[(0.00218)(731) – (3.075)(0.7515)]
= 127.0
Critical Properties
Critical properties are of interest because they are used to
find reduced conditions of temperature and pressure as re-
quired for corresponding states correlations. Pseudo-critical
properties are used in many corresponding states correlations
for mixtures.
The following equations taken from the API Technical Data
Book36a,b estimate pseudo-critical temperature and pressure
for petroleum fractions (pseudo, or undefined components):
Ppc = 3.12281(109) T-2.3125 S 2.3201 Eq 23-15
Tpc = 24.2787 T0.58848 S0.3596 Eq 23-16
These equations are in terms of T = MeABP (°R) and specific
gravity, S, at 60 °F. Both of these correlations are valid over
the range of 80 to 690 molecular weight; 70 to 295°F normal
boiling point; and 6.6° to 95° API.
Example 23-6 — Pseudo-critical temperature and pressure.
Take the previous mixture (from Example 23-4) with:
VABP = 325 °F
MeABP = 271°F
API = 56.8°
MW = 127 (Ex. 23-5)
ASTM D-86, 10% to 90% Slope = 5.49
Find its pseudo-critical temperature.
Solution Steps
From Fig. 23-18 with ASTM D-86 slope = 5.49 find a VABP
correction of about –85°F (extrapolated from the left-hand
group).
MABP = 325- 85 = 240°F
Use Eq 23-16 to calculate the pseudo-critical temperature:
Tpc = 24.2787 (271 + 460)0.58848
(0.7515)0.3596 = 1062 °R or 602 °F
For this 56.8° API fluid, estimate the pseudo-critical pres-
sure, using Eq 23-15 and MeABP = 271°F:
Ppc = 3.12281(109) (271 + 460)-2.3125 (0.7515)2.3021 = 386 psia
23-27
Acentric Factor
The acentric factor, ω, is often a third parameter in corre-
sponding states correlations. Figure 23-2 tabulates it for pure
hydrocarbons. The acentric factor is a function of Pvp, Pc, and
Tc. It is arbitrarily defined as
ω = -log(Pvp/Pc)Tr=0.7-1.0 Eq 23-17
This definition requires knowledge of the critical (pseudo-
critical) temperature, vapor pressure, and critical (pseudo-
critical) pressure.
For a hydrocarbon mixture of known composition that con-
tains similar components, a reasonably good estimate for the
acentric factor is the molar average of the individual pure com-
ponent acentric factors:
ω = ∑ yiω i Eq 23-18
i
If the vapor pressure is not known, ω can be estimated38 for
pure hydrocarbons or for fractions with boiling point ranges of
50°F or less using:
3  log Pc – log 14.7 
ω =   –1.0 Eq 23-19
7 (Tc ⁄ Tb) – 1 
Example 23-7 — Acentric factor.
A narrow-boiling petroleum fraction has a VABP of 418°F,
an ASTM slope of 0.75 and an API gravity of 41°. Estimate its
acentric factor. To use Eq 23-19 we need the average boiling
point (MeABP); the pseudo-critical temperature (a function of
MABP); and the pseudo-critical pressure (a function of Me-
ABP).
From Fig. 23-18, the correction to VABP for mean average
is –3°F; the correction for MABP is –5°F. Note that for narrow-
boiling fractions, all boiling points approach the volumetric
average. Then, MeABP = 415°F and MABP is 413°F.
From Eq. 23-15, the pseudo-critical pressure is:
T = 415 + 460 = 875 °R
S for 41° API = 141.5/(131.5 + 41) = 0.871
Ppc = 3.12281(109) (875)-2.3125(0.871)2.3201 = 356 psia
From Eq 23-16, the pseudo-critical temperature is:
Tpc = 24.2787(875)0.58848(0.871)0.3596 = 1244 °R
3  log (356) – log (14.7) 
ω = –1.0 = 0.407
7  (1244/875) – 1.0 
Vapor Pressure
The vapor pressures of light hydrocarbons and some com-
mon inorganics in the temperature range below 100°F appear
in Fig. 23-19. Vapor pressures at higher temperatures, up to
600°F, are in Fig. 23-20 for the same compounds. Note that,
except for ethylene and propylene, the hydrocarbons are all
normal paraffins.
VISCOSITY
Figures 23-21 through 23-29 give the viscosity of hydrocar-
bon liquids and vapors, water, steam, and miscellaneous gases.
Figure 23-21 gives data on hydrocarbon liquids. Figures 23-
22, 23-23 and 23-24 present data on hydrocarbon gases. To
correct for pressure, adjust the gas viscosity from Fig. 23-22
from atmospheric pressure using Fig. 23-24, or read directly
 FIG. 23-19
Low-Temperature Vapor Pressures for Light Hydrocarbons

23-28
 FIG. 23-20
High-Temperature Vapor Pressures for Light Hydrocarbons

23-29
 FIG. 23-21
Viscosities of Hydrocarbon Liquids

23-30
 FIG. 23-22
Viscosity of Paraffin Hydrocarbon Gases at One Atmosphere

from Fig. 23-23. Figure 23-24 is better when the reduced tem- Hence, the viscosity at 1000 psia and 100°F is:
perature is greater than 1.0. Figure 23-28 gives the viscosity
of hydrocarbon liquids containing dissolved gases. Note that µ = (1.21) (0.0105) = 0.0127 centipoise
Fig. 1-7 gives conversion factors for viscosity. The method of Dean and Stiel41 is best for calculating the
viscosity of a gaseous mixture with large amounts of non-hy-
Calculation of Gas Mixture Viscosity drocarbons. This method is particularly useful for handling
Example 23-8 — Determine the viscosity of a gas at 1,000 psia natural gas with high CO2 content. Compared to 30 CO2-N2
and 100 °F with the properties: MW = 22, Tc = 409°R, Pc = 665 mixtures, this method has an average deviation of 1.21% at
psia. pressures up to 3525 psia. The method uses a factor, ξ, defined
as:
Solution Steps
Gid = 22/28.9625 = 0.760
From Fig. 23-22 at 100 °F:
µA = 0.0105 centipoise Eq 23-20
Then:
100 + 459.67 1000
Tr = = 1.37 Pr = = 1.50 If Tr > 1.5, then
409 665
Note: If the composition of the gas is available, calculate the ξµA = 166.8(10-5)(0.1338 Tr -0.0932)5/9 Eq 23-21
pseudo-critical temperatures and pressures as outlined in this
If Tr ≥ 1.5,
section.
Because Tr > 1.0, Fig. 23-24 is better than Fig. 23-23 to obtain ξµA = 34.0(10-5) (Tr8/9 ) Eq 23-22
the correction for elevated pressure to the viscosity at one at-
mosphere. In either case, µA is ξµA divided by ξ.
From Fig. 23-24: Equations 23-20 through 23-22 predict the viscosity of pure
gases as well as mixtures. To apply the Dean and Stiel41
µ/µA = 1.21 method to mixtures, calculate the pseudo-critical volumes, Z-

23-31
 FIG. 23-23
Hydrocarbon Gas Viscosity

23-32
 FIG. 23-24
Viscosity Ratio vs. Pseudoreduced Temperature

FIG. 23-25 FIG. 23-26

Viscosity of Miscellaneous Gases – One Atmosphere Viscosity of Air43, 44, 45

23-33
 FIG. 23-27 Because Tr > 1.5, the expression for ξµA is Eq 23-21.
Water Viscosity at Saturated Conditions ξµA = 166.8(10-5)(0.1338 Tr - 0.0932)5/9
= 166.8(10-5) [(0.1338) (1.517) -0.0932]5/9
= 48.91(10-5)
µΑ = 0.01138 centipoise
Using Fig. 23-22 and correcting for the nitrogen and carbon
dioxide content of this mixture gives µa = 0.0116 cp. This is a
good check. Had this example contained a 20% N2 content, the
N2 range of Fig. 23-22 would be exceeded and dictate use of
the Dean and Stiel method. When conditions fall within the
limits of Fig. 23-23, use this figure and not the Dean and Stiel
correlation.
Viscosity of Petroleum Fractions
Mid-Boiling Point Method — The viscosity of a crude oil
or crude oil fraction can be estimated if the mid-boiling point
and gravity are known:
Mid-boiling point is defined as the boiling point at 50% vol-
ume distilled.
η = A•e(1.8B/T) Eq 23-27
A = (101.78Tb-0.175 – 29.263)KW/B Eq 23-28
In (B) = 4.717 + 0.00292 Tb Eq 23-29
Example 23-10 — At l00°F and 210°F find the viscosity of a
heavy condensate having a mid-boiIing point of 325°F and a
specific gravity of 0.7688.
Solution Steps
3

√ 
325 + 459.67
KW = = 11.99
0.7688
ln(B) = 4.717 + 0.00292(325 + 459.67) = 7.01
B = 1105.7
factors, and temperatures using the Prausnitz and Gunn42
mixing rules: A = [ 101.78(325 + 459.67)-0.175 – 29.263](11.99/1105.3)
= 0.02645
The same constants apply at 100°F and at 210°F.
Vcm = ∑ yiVci Eq 23-23
i h = 0.02645•e[1.8(1105.7)/559.67 ]= 0.926 cs at 100°F
h = 0.02645•e[1.8(1105.7)/669.67 ] = 0.517 cs at 210°F
Zcm = ∑ yiZci Eq 23-24
The reported experimental values are 0.93 and 0.52 centis-
i
tokes, respectively.
Tcm = ∑ yiTci Eq 23-25
i THERMAL CONDUCTIVITY
ZcmRTcm Thermal conductivity for natural gas mixtures at elevated
Pcm = Eq 23-26
Vc m pressure can be calculated from an atmospheric value and a
pressure correction. Figs. 23-31 through 23-36 present low
Example 23-9 — For a temperature of 50 °F and a pressure of pressure thermal conductivity data for gases developed from
300 psia, estimate the viscosity of a mixture of 80 mol% meth- published data51, 54. The pressure correction of Lenoir et al.52
ane, 15 mol% nitrogen, and 5 mol% carbon dioxide. Fig. 23-30 shown in Fig. 23-32 applies to these low pressure data. The
summarizes the calculations: thermal conductivity of liquid paraffin hydrocarbons appears
Pcm = ZcmRTcm/Vcm = (0.2877)(10.73)(335.9)/1.562 = in Fig. 23-35 and the thermal conductivity of liquid petroleum
663.4 psia fractions appears in Fig. 23-36.
Example 23-11 — Find the thermal conductivity of a natural
Substituting from the calculation table in Fig. 23-30 into Eq gas at 700 psia and 300 °F with properties MW = 25, Tc = 440
23-20: °R and Pc = 660 psia.
ξ = (5.4402)(335.9)1/6/[(19.237)1/2(663.4)2/3 = 0.043 Solution Steps
Tr = T/Tcm = 509.7/335.9 = 1.517 From Fig. 23-31, at 300°F:

23-34
 FIG. 23-28
Liquid Viscosity of Pure and Mixed Hydrocarbons Containing Dissolved Gases at 100°F and One Atmosphere

23-35
 FIG. 23-29 ductivity of each component at the given temperature is read
46, 47 from the charts provided and the thermal conductivity of the
Viscosity of Steam
mixture is determined by the "cube root rule56.” This rule is
applicable to mixtures of simple gases; it does not apply to
mixtures containing CO2 because its thermal conductivity
goes through a maximum.

Eq 23-30

Compared to 17 systems56, the cube root rule has an average

deviation of 2.7%. The method of Li55 based upon volume frac-
tions works best for the thermal conductivity of a liquid mix-
ture.
Example 23-12 — Find the thermal conductivity of the gase-
ous mixture shown in Fig. 23-37 at 200 °F and one atmos-
phere.
km = 0.05774/2.822 = 0.0205 Btu/[(hr ft2 °F)/ft]

TRANSPORT PROPERTY REFERENCES

No simple correlations exist for the transport properties of
viscosity and thermal conductivity. For pure components, the
best approach is a complicated equation with many constants
that must be fit to experimental data, or extensive tables. Var-
gaftik62 and Touloukian65 each have extensive collections of
experimental data.

SURFACE TENSION
The interior molecules of a liquid exert an inward force of
attraction upon the surface molecules that tends to minimize
the surface area of the liquid. The work required to enlarge
the surface area by one square centimeter is the surface free
energy. The perpendicular force in the liquid surface, called
kA = 0.0248 Btu/[(hr ft2 °F)/ft] surface tension, exerts a force parallel to the plane of the sur-
face. Surface tension is an important property for wetting,
Tr= (300 + 459.67)/440 = 1.73 foaming, emulsification, and droplet formation and is used in
Pr = 700/660 = 1.06 the design of fractionators, absorbers, two-phase pipelines,
and in reservoir calculations.
From Fig. 23-32:
Pure Components
k/kA = 1.15 Figure 23-38 provides the surface tension of pure hydrocar-
2 bons as a function of temperature.
k = (1.15) (0.0248) = 0.0285 Btu/[(hr ft °F)/ft]
Stiel and Thodos53 present another method for estimating Mixtures
thermal conductivity. To determine the thermal conductivity Surface tension for binaries of known composition at or near
of a gaseous mixture of defined components, the thermal con- amospheric pressure may be calculated78 using:

FIG. 23-30
Calculation of Viscosity of a Gas Mixture

Mole Molecular Pci, Vci = MWi • vci Pci • Vci

Tci, °R Vci, ft3/lb Zci =
Fraction, yi Weight, MWi psia ft3/lb mole 10.73 • Tci
CH4 0.80 16.043 667.0 343.0 0.0988 1.59 0.2882
N2 0.15 28.013 492.8 227.2 0.0510 1.43 0.2891
CO2 0.05 44.010 1069.5 547.4 0.0342 1.51 0.2749
Mixture 1.00 19.237 — 335.9 — 1.562 0.2877
Σ MWcm = Σyi • MWi Tcm = Σyi • Tci Vcm = Σyi • Vci Zcm = Σyi • Zci

23-36
 FIG. 23-31 FIG. 23-33
Thermal Conductivity of Natural and Hydrocarbon Gases Thermal Conductivity of Miscellaneous Gases
at One Atmosphere (14.696 psia) at One Atmosphere59, 60, 61, 62

FIG. 23-32
Thermal Conductivity Ratio for Gases

FIG. 23-34
Thermal Conductivity of Hydrocarbon Gases
at One Atmosphere67, 68, 69

23-37
 FIG. 23-35
Thermal Conductivity of Liquid Paraffin Hydrocarbons

FIG. 23-36
Thermal Conductivity of Liquid Petroleum Fractions58

23-38
 σm = (σ1σ2)/(σ1x2 + σ2x1) Eq 23-31
The presence of inert gases, such as N2 and CO2, in the liquid
phase tends to lower the surface tension of the liquid. When
the concentration of inert gases in the liquid exceeds 1.0 mol%,
estimated values of surface tension may be 5 to 20% higher
than actual values for the mixture.
GROSS HEATING VALUE OF
NATURAL GASES
A complete compositional analysis of the mixture permits
calculation of the gross heating value, specific gravity, and Z-
factor of a natural gas mixture. Some definitions are in order
before starting this discussion. It is necessary to understand
the concepts: real gas, ideal gas, gross heating value (higher
heating value, higher calorific value), net heating value (lower
heating value, lower calorific value), hypothetical state.
Real Gas — refers to an actual fluid in its vapor phase. It
is possible to collect samples of these fluids and to measure
their thermophysical properties.
Hypothetical State — refers to a definition of a fluid in a
state that cannot actually exist, e.g. methane as a liquid at 60
°F and 14.696 psia. Methane cannot be in its liquid phase at
this temperature and pressure, but such a state, when defined,
can be used in calculations. Unfortunately, it is not possible
to find an unambiguously suitable numerical value for meth-
ane properties at these conditions.
Ideal Gas — refers to a hypothetical state in which a fluid
behaves in a particularly simple manner. A simple equation
of state describes an ideal gas exactly. The ideal gas is a useful
concept even if the state cannot be achieved because an unam-
biguous path exists to reach the state starting with a real fluid.
Gross Heating Value — by definition is the total energy
transferred as heat in an ideal combustion reaction at a stand-
ard temperature and pressure in which all water formed ap-
pears as liquid. The gross heating is an ideal gas property in
a hypothetical state (the water cannot all condense to liquid
because some of the water would saturate the CO2 in the prod-
ucts):
Hvid = ∑ yiHvidi Eq 23-32
i
Values for Hvid and MWi are in Fig. 23-2.
Calculation of the ideal energy flow requires multiplication
of the gross heating value by the ideal gas volumetric flow rate
of gas for the time period. To employ a real gas flow to calcu-
late the ideal energy flow requires converting the real gas flow
rate to the ideal gas flow rate by dividing by the Z-factor. Often
the heating value Hvid appears in tables divided by the Z-fac-
tor in preparation for multiplying by the real gas flow rate.
Thus, Hvid/Z is the ideal gross heating value per unit volume
of real gas. Note that the Z-factor must be determined for the
natural gas mixture and then divided into the gross heating
value of the mixture. It is not correct to divide each pure com-
ponent gross heating value by the pure component Z-factor
and then take the molar average.
Net Heating Value — by definition is the total energy
transferred as heat in an ideal combustion reaction at a stand-
ard temperature and pressure in which all water formed ap-
pears as vapor. The net heating is an ideal gas property in a
hypothetical state (the water cannot all remain vapor because,
after the water saturates the CO2 in the products, the rest
23-39
would condense). It is a common misconception that the net
heating value applies to industrial operations such as fired
heaters and boilers. While the flue gases from these operations
do not condense, the net heating value does not apply directly
because the gases are not at 60°F. Were the gases to cool to
60°F, some of the water would condense while the remainder
would saturate the gases. It is possible to use either the gross
or net heating value in such situations taking care to utilize
the hypothetical state properly.
Cost of Gas — comes from a simple accounting equation
Eq 23-33
This equation shows that for custody transfer it is not nec-
essary to use real gas heating values (real gas heating values
could be calculated from the ideal gas values using well known,
but computationally intense methods). If the price is set by
contract, it is possible to set either a real gas price or an ideal
gas price. For the former, it is necessary to use real gas values;
for the latter, the ideal gas values are correct. Because it is
much simpler to obtain the ideal gas values, it is preferable to
establish contracts based upon the ideal gas values. The ideal
gas flow rate comes from the real gas flow rate
Eq 23-34
because the Z-Factor is the ratio of the real gas volume to the
ideal gas volume.
This paragraph represents the justification for using the
GPA property tables for custody transfer. The GPA tables pre-
sent ideal gas properties that are more accurate to use in mix-
ture calculations and easier to present in tables than real gas
properties.
Z-Factor — when dealing with custody transfer of natural
gas, it is common to use a simple equation of state for calcula-
tions because the base pressure (at which transfer occurs by
definition) is near atmospheric. The equation is
Z = 1+ BP / RT Eq 23-35
It is common to assume that
2
N 
–B ⁄ RT = ∑ xi bi Eq 23-36
i = 1 
 
and
bi = √

–B / RT Eq 23-37
This Z-Factor is sufficiently accurate at low pressure for cal-
culations involving natural gas mixtures.
Specific gravity (also termed relative density or gas grav-
ity) – by definition is the ratio of gas density (at the tempera-
ture and pressure of the gas) to the density of dry air (at the
air temperature and pressure).
G = ρ / ρa = (PTaZa / PaTZ) (MW / MWa) Eq 23-38
The ideal gas specific gravity is the ratio of the molecular
weight of the gas to the molecular weight of dry air.
Gid = MW/MWa
For a mixture
Gid = ∑ yiGidi Eq 23-39
i
 FIG. 23-37
Calculation of Thermal Conductivity

Thermal
Mole Molecular 3 3 3
Component
Fraction
Conductivity
Weight √
 MWi (yi √
MW  i) (yi ki 
√
MWi )
Btu/[(hr • sq ft • °F)/ft]
CO2 0.10 0.0127 44.010 3.530 0.3530 0.00448
H2S 0.20 0.0136 34.076 3.242 0.6484 0.00882
N2 0.05 0.0175 28.013 3.037 0.1519 0.00266
CH4 0.60 0.0258 16.043 2.522 1.5132 0.03904
C2H6 0.05 0.0176 30.070 3.109 0.1555 0.00274
Total 1.00 2.8220 0.05774

FIG. 23-38
Surface Tension of Paraffin Hydrocarbons85

23-40
 The specific gravity G is measured and is generally used to FIG. 23-39
calculate the molecular weight ratio Gid when the gas compo-
sition is not available. Specific Heat for 0.58 Specific gravity gas (16.7 MW)

Gid = MW/MWa = GPaTZ / PTaZa Eq 23-40

The temperatures and pressures used must correspond to

actual measurement conditions or serious errors in Gid can
occur.

Corrections for Water Content — When the gas contains

water, but the component analysis is on a dry basis, the com-
ponent analysis must be adjusted to reflect the presence of
water. The mole fraction of water in the mixture is estimated
from the definition of relative humidity:

yw = hgPσw ⁄ P = nw ⁄ (1 + nw)
(on a one mole basis) Eq 23-41

where hg is the relative humidity of the gas (hg = 1 for satu-

rated gas). Rearranging Eq 23-41 for the moles of water:

nw = yw ⁄ (1 + yw) Eq 23-42

Then, the corrected mole fractions of the gas become:

FIG. 23-40
 1   1 
yi(cor) = yi 
1 + n  = yi  1 + y /(1 y  = (1 – yw)yi Specific Heat for 0.75 Specific gravity gas (21.6 MW)
 w   w w) 
Eq 23-43

and the gross heating value becomes:

Hvid = (1 – yw) ∑ yiHvid

i Eq 23-44
i

If the compositional analysis determines water as a compo-

nent, and the summation contains the water term, the heating
value becomes:

Hvid = ∑ yiHvidi – yw Hvid

w Eq 23-45
i

We remove the effect of water because, although water has

a heating value (the ideal enthalpy of condensation), we as-
sume that the water carried by wet gas (spectator water) does
not condense while we assume that the water formed by the
reaction does condense.

Accounting for water using Eqs 23-41 through Eq 23-45 is

sufficient for custody transfer purposes because the contract-
ing parties can agree to accept the hypothetical state for the SPECIFIC HEAT
gross heating value. When trying to model actual situations,
the question becomes more complex. It is obvious that all the Figs. 23-39 and 23-40 present specific heat curves for two
water formed in a reaction cannot condense because in a situ- different gas mixtures. These curves are not based on experi-
ation in which both air and gas are dry, some of the reaction mental data but were developed using calculated values from
water must saturate the product gases while the remainder a process simulator. These charts should give reasonable re-
condenses. It is possible to account for these effects, but those sults for quick calculations of sensible heating/cooling.
interested should consult GPA Standard 2172, "Calculation of
Gross Heating Value, Relative Density and Compressibility
Factor for Natural Gas Mixtures from Compositional Analy-
sis," for the analysis. This standard contains additional de-
tails and examples covering all these calculation methods.
GPA 2172 contains a listing of the Basic source code for a com-
puter program to perform the calculations.

23-41
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