SECTION 23

Physical Properties
This section contains a number of charts, correlations, and
procedures for the prediction of physical properties of hydro-
carbons and components found with them. Fig. 23-1 lists the
nomenclature used in this section.
Fig. 23-2 is a table containing frequently used physical prop-
erties for a number of hydrocarbons and other selected com-
ponents. Immediately following is a detailed list of references
and footnoted explanation for the values in Fig. 23-2.
Physical properties for eighteen selected compounds can be
found in GPA Standard 2145, “Table of Physical Constants of
Paraffin Hydrocarbons and Other Components of Natural
Gas.”

FIG. 23-1
Nomenclature

B = second virial coefficient for a gas mixture, W = mass, lb

(psia)-1 WABP = weight average boiling point, °F
B′ = mole fraction H2S in sour gas stream, Eq 23-6 yi = mole fraction of component i from analysis on dry
Bii = second virial coefficient for component i basis, Eq 23-37
Bij = second cross virial coefficient for components i x = mole fraction in liquid phase
and j ywi = mole fraction of component i adjusted for water
bi1/2 = summation factor for component i content
CABP = cubic average boiling point, °F y = mole fraction in gas phase
d = density, g/cc Z = compressibility factor
G = specific gravity or relative density (gas density) Greek
Gi = specific gravity (gas gravity) of ideal gas, MW/MWa
ε = pseudocritical temperature adjustment factor,
Gid
i = molecular weight ratio of component i in mixture Eq 23-6
Hv = gross heating value per unit volume of ideal gas, θ = MeABP/T pc
Btu/cu ft ρ = density, lb/cu ft
Kw = Watson characterization factor, Fig. 23-12
µ = viscosity at operating temperature and pressure,
k = thermal conductivity, Btu/[(hr • sq ft • °F)/ft] centipoise
ka = thermal conductivity at one atmosphere,
µA = viscosity at 14.7 psia (1 atm) and operating
Btu/[(hr • sq ft • °F)/ft]
temperature, centipoise
M = mass fraction
ξ = factor defined by Eq 23-20
m = mass, lb
σ = surface tension, dynes/cm
MW = molecular weight, lb/lb mole
ω = acentric factor
MABP = molal average boiling point, °F or °R
MeABP = Mean average boiling point, °F or °R η = kinematic viscosity, centistokes
n = number of moles, (mass/Mole weight) Subscripts
P = pressure, psia a = air
Pc′ = pseudocritical pressure adjusted for acid gas b = boiling
composition, psia c = critical
Pvp = vapor pressure at a reduced temperature of 0.7 i = component i
Pwo = vapor pressure of water, 0.25636 psia at 60°F L = liquid
R = gas constant, 10.73 (psia • cu ft)/(°R • lb mole) for m = mixture
all gases (see Section 1 for R in other units) pc = pseudocritical
S = specific gravity at 60°/60°F r = reduced state
T = absolute temperature, °R V = vapor
t = ASTM D-86 distillation temperature for a given v = volume
volumetric fraction, °F or °R, Eq 23-11 w = water
Tc′ = pseudocritical temperature adjusted for acid gas Superscripts
composition, °R id = ideal gas
V = volume, cu ft w = water
VABP = volumetric average boiling point, °F o = reference state

23-1
 FIG. 23-2
Physical Constants

23-2
FIG. 23-2 (Cont’d)
Physical Constants

23-3
FIG. 23-2 (Cont’d)
Physical Constants

23-4
 FIG. 23-2 (Cont’d)
Notes and References for the Table of Physical Constants

23-5
 FIG. 23-2 (Cont’d)
Notes and References for the Table of Physical Constants

23-6
 FIG. 23-2 (Cont’d)
Notes and References for the Table of Physical Constants

23-7
 FIG. 23-2 (Cont’d)
Notes for the Table of Physical Constants

a. Values in parentheses are estimated values. p. An extrapolated value.

b. The temperature is above the critical point. q. Gas at 60°F and the liquid at the normal boiling point.
c. At saturation pressure (triple point). r. Fixed points on the 1968 International Practical Temperature
d. Sublimation point. Scale (IPTS-68).
e. The + sign and number following specify the number of cm3 of s. Fixed points on the 1990 International Temperature Scale
TEL added per gallon to achieve the ASTM octane number of (ITS-90).
100, which corresponds to that of Isooctane (2,2,4-
Trimethylpentane). t. Densities at the normal boiling point are: Ethane, 4.540 [29];
Propane, 4.484 [28]; Propene, 5.083 [5]; Hydrogen Chloride,
f. These compounds form a glass.
9.948 [43]; Hydrogen Sulfide, 7.919 [25]; Ammonia, 5.688 [43];
g. Average value from octane numbers of more than one sample. Sulfur Dioxide, 12.20 [43].
h. Saturation pressure and 60°F.
u. Technically, water has a heating value in two cases: net (–1060.
i. Index of refraction of the gas. Btu/lb) when water is liquid in the reactants, and gross
j. Densities of the liquid at the normal boiling point. (+50.313 Btu/ft3) when water is gas in the reactants. The value
k. Heat of sublimation. is the ideal heat of vaporization (enthalpy of the ideal gas less
m. Equation 2 of the reference was refitted to give: the enthalpy of the saturated liquid at the vapor pressure).
a = 0.7872957; b = 0.1294083; c = 0.03439519. This is a matter of definition; water does not burn.
n. Normal hydrogen (25% para, 75% ortho). v. Extreme values of those reported by reference 19.

A. Molar mass (molecular weight) is based upon the following
atomic weights: C = 12.011; H = 1.00794; O = 15.9994; N =
14.0067; S = 32.066; Cl = 35.4527. The values were rounded
off after calculating the molar mass using all significant figures
in the atomic weights.
B. Boiling point: the temperature at equilibrium between the liq-
uid and vapor phases at 14.696 psia.
C. Freezing point: the temperature at equilibrium between the crys-
talline phase and the air saturated liquid at 14.696 psia.
D. The refractive index reported refers to the liquid or gas and is
measured for light of wavelength corresponding to the sodium
D-line (589.26 nm).
E. The relative density (specific gravity): ρ(liquid, 60°F)/ρ(water,
60°F). The density of water at 60°F is 8.3372 lb/gal.
F. The temperature coefficient of density is related to the expan-
sion coefficient by: (∂ρ/∂T)P/ρ = –(∂ρV/∂T)P/V, in units of 1/T.
G. Pitzer acentric factor: ω = –log10(P/Pc) –1, P at T = 0.7 Tc
H. Compressibility factor of the real gas, Z = PV/RT, is calculated
using the second virial coefficient.
I. The density of an ideal gas relative to air is calculated by di-
viding the molar mass of the of the gas by 28.9625, the calcu-
lated average molar mass of air. See ref. 34 for the average
composition of dry air. The specific volume of an ideal gas is
calculated from the ideal gas equation. The volume ratio is:
V(ideal gas)/V(liquid in vacuum).
J. The liquid value is not rigorously CP, but rather it is the heat ca-
pacity along the saturation line CS defined by: CS = CP – T
(∂V/∂T)P(∂P/∂T)S. For liquids far from the critical point, CS ≈ CP.
K. The heating value is the negative of the enthalpy of combustion
at 60°F and 14.696 psia in an ideal reaction (one where all
gasses are ideal gasses). For an arbitrary organic compound,
the combustion reaction is:
CnHmOhSjNk (s,l,or,g) + (n + m/4 – h/2 + j ) O2(g) →
n CO2(g) + m/2 H2O (g or l) + k/2 N2(g) + j SO2(g),
where s, l and g denote respectively solid, liquid and ideal gas.
For gross heating values, the water formed is liquid; for net
heating values, the water formed is ideal gas. Values reported
are on a dry basis. To account for water in the heating value,
see GPA 2172. The Btu/lb or gal. liquid column assumes a re-
action with the fuel in the liquid state, while the Btu/ft3 ideal
gas column assumes the gas in the ideal gas state. Therefore,
the values are not consistent if used in the same calculation,
e.g. a gas plant balance.
L. The heat of vaporization is the enthalpy of the saturated vapor
at the boiling point at 14.696 psia minus the enthalpy of the
saturated liquid at the same conditions.
M. Air required for the combustion of ideal gas for compounds of
formula CnHmOhSjNk is:
V(air)/V(gas) = (n + m/4 ( h/2 + j)/0.20946.

COMMENTS
Units: reported values are based upon the following units with energy: British thermal unit (I.T.)
their equivalent corresponding SI units: Btu = 251.9958 cal (I.T.) = 1055.056 J
mass: Pound (avdp), lbm = 0.45359237 kg Gas constant, R:
length: foot, ft = 0.3048 m 1.985887 Btu (I.T.)/(R lb mol)
temperature: degree Fahrenheit 10.73164 ft3 psia/(R lb mol)
t/°F) = 32 = [1.8(t/°C)]. 8.314510 J/(K(mol)
The Celsius scale is defined by the International Temperature Conversion factors:
of 1990 (ITS-90), where 0°C = 273.15 K.
1 ft3 = 7.480520 gal.
Other derived units are:
volume: cubic foot, ft3 = 0.02831685 m3 1 lbm/ft3 = 0.1336806 lbm/gal = 16.018462 kg/m3
gallon = 231 in3 = 0.0037854512 m3 1 psia = 0.06804596 atm = 6.894757 kPa
pressure: pound per square inch absolute 1 atm = 14.69595 psia = 760 Torr = 101.3250 kPa
psia = 6894.757 kPa 1 Btu (I.T.) = 252.1644 calth

23-8
 FIG. 23-2 (Cont’d)
References for the Table of Physical Constants
1. Ambrose, D., National Physical Laboratory, Teddington, Mid-
dlesex, England: Feb. 1980, NPL Report Chem 107.
2. Ambrose, D.; Hall, D. J.; Lee, D. A.; Lewis, G. B.; Mash, C. J.,
J. Chem. Thermo., 11, 1089 (1979).
3. Angus, S.; Armstrong, B.; de Reuck, K. M., Eds. “Carbon Diox-
ide. International Thermodynamic Tables of the Fluid State-3,”
Pergamon Press: Oxford, 1976.
4. Angus, S.; Armstrong, B.; de Reuck, K. M., Eds. “Methane. In-
ternational Thermodynamic Tables of the Fluid State-5,” Per-
gamon Press: Oxford, 1978.
5. Angus, S.; Armstrong, B.; de Reuck, K. M., “Propylene
(Propene). International Thermodynamic Tables of the Fluid
State-7,” Pergamon Press: Oxford, 1980.
6. Angus, S.; de Reuck, K. M.; Armstrong, B., Eds. “Nitrogen. In-
ternational Thermodynamic Tables of the Fluid State-6,” Per-
gamon Press: Oxford, 1979.
7. Angus, S.; de Reuck, K. M.; McCarthy, R. D., Eds. “Helium.
International Thermodynamic Tables of the Fluid State-4,”
Pergamon Press: Oxford, 1977.
8. Armstrong, G. T.; Jobe, T. L., “Heating Values of Natural Gas
and its Components,” NBSIR 82-2401, May 1982.
9. Aston, J. G.; Szasz, G. J.; Finke, H. L., J. Am. Chem. Soc., 65,
1135 (1943).
10. Barber, C. R., Metrologia 5, 35 (1969).
11. Boundy, R. H.; Boyer, R. F., (Eds.), “Styrene, Its Polymers, Co-
polymers and Derivatives,” A.C.S. monograph No. 115, Rein-
holt, N.Y., 1952.
12. Chaiyavech, P.; Van Winkle, M., J. Chem. Eng. Data, 4, 53
(1959).
13. Chao, J.; Hall, K. R.; Yao, J., Thermochimica Acta, 64, 285
(1983).
14. CODATA Task Group on Key Values for Thermodynamics, CO-
DATA Special Report No. 7, 1978.
15. Commission on Atomic Weights and Isotopic Abundances, Pure
and Appl. Chem. 63, 975 (1991).
16. Dean, J. W., “A Tabulation of the Properties of Normal Hydro-
gen from Low Temperature to 300 K and from 1 to 100 Atmos-
pheres,” NBS Tech. Note 120, November 1961.
17. Douslin, D. R.; Huffman, H. M., J. Am. Chem. Soc., 68, 1704
(1946).
18. Edwards, D. G., “The Vapor Pressure of 30 Inorganic Liquids
Between One Atmosphere and the Critical Point,” Univ. of
Calif., Lawrence Radiation Laboratory, UCRL-7167. June 13,
1963.
19. Engineering Sciences Data Unit, “EDSU, Engineering Sci-
ences Data,” EDSU International Ltd., London.
20. Flebbe, J. L.; Barclay, D. A.; Manley, D. B., J. Chem. Eng. Data,
27, 405 (1982).
21. Francis, A. W., J. Chem. Eng. Data, 5, 534 (1960).
22. Ginnings, D. C.; Furukawa, G. T., J. Am. Chem. Soc. 75, 522
(1953).
23. Girard, G., “Recommended Reference Materials of the Realiza-
tion of Physicochemical Properties,” Chapter 2, Marsh, K. N.
Ed.; Blackwell Sci. Pub.: London, 1987.
23-9
24. Glasgow, A. R.; Murphy, E. T.; Willingham, C. B.; Rossini, F. D.,
J. Res. NBS, 37, 141 (1946).
25. Goodwin, R. D., “Hydrogen Sulfide Provisional Thermochemi-
cal Properties from 188 to 700 K at Pressures to 75 MPa,”
NBSIR 83-1694, October 1983.
26. Goodwin, R. D.; Haynes, W. M., “Thermophysical Properties of
Isobutane from 114 to 700 K at Pressures to 70 MPa,” NBS
Tech. Note 1051, January 1982.
27. Goodwin, R. D.; Haynes, W. M., “Thermophysical Properties of
Normal Butane from 135 to 700 K at Pressures to 70 MPa,”
NBS Monograph 169, April 1982.
28. Goodwin, R. D.; Haynes, W. M., “Thermophysical Properties of
Propane from 85 to 700 K at Pressures to 70 MPa,” NBS Mono-
graph 170, April 1982.
29. Goodwin, R. D.; Roder, H. M.; Straty, G. C.; “Thermophysical
Properties of Ethane, 90 to 600 K at Pressures to 700 bar,” NBS
Tech. Note 684, August 1976.
30. Guthrie, G. B.; Huffman, H. M., J. Am. Chem. Soc., 65, 1139
(1943).
31. Haar, L.; Gallagher, J. S.; Kell, G. S., “NBS/NRC Steam Tables,”
Hemisphere Publishing Corporation, Washington, 1984.
32. Huffman, H. M.; Park, G. S.; Thomas, S. B., J. Am. Chem. Soc.,
52, 3241 (1930).
33. Hust, J. G.; Stewart, R. B., “Thermodynamic Property Values
for Gaseous and Liquid Carbon Monoxide from 70 to 300 At-
mospheres,” NBS Technical Note 202, Nov. 1963.
34. Jones, F. E., J. Res. NBS, 83, 419 (1978).
35. Keenan, J. H.; Chao, J.; Kaye, J. “Gas Tables: (SI Units),” John
Wiley and Sons, Inc.: New York, 1983.
36. “The Matheson Unabridged Gas Data Book,” Matheson Gas
Products; New York, 1974.
37. McCarty, R. D.; Weber, L. A., “Thermophysical Properties of
Oxygen from the Freezing Liquid Line to 600 R for Pressures
to 5000 Psia,” NBS Technical Note 384, July 1971.
38. Messerly, J. F.; Guthrie, G. B.; Todd, S. S.; Finke, H. L., J. Chem.
Eng. Data, 12, 338 (1967).
39. Messerly, J. F.; Todd, S. S.; Guthrie, G. B., J. Chem. Eng. Data,
15, 227 (1970).
40. Ohe, S., “Computer Aided Data Book of Vapor Pressure,” Data
Book Publishing Co., Tokyo, Japan, 1976.
41. Roder, H. M., “Measurements of the Specific Heats, Cs, and Cv,
of Dense Gaseous and Liquid Ethane,” J. Res. Nat. Bur. Stand.
(U.S.) 80A, 739 (1976).
42. Scott, R. B.; Meyers, C. H.; Rands, R. D.; Brickwedde, F. G.;
Bekkedahl, N., J. Res. NBS, 35, 39 (1945).
43. Stull, D. R.; Westrum, E. F.; Sinke, G. C., “The Chemical Ther-
modynamics of Organic Compounds,” John Wiley & Sons, Inc.,
New York, 1969.
44. “TRC Thermodynamic Tables ( Hydrocarbons,” Thermodynam-
ics Research Center, Texas A&M University System: College
Station, Texas.
45. “TRC Thermodynamic Tables ( Non-Hydrocarbons,” Thermo-
dynamics Research Center, Texas A&M University System:
College Station, Texas.
 The table in Fig. 23-2 is followed by procedures for estimat-
ing compressibility for gases. Additional material follows on
hydrocarbon fluid densities, boiling points, ASTM distillation,
critical properties, acentric factors, vapor pressures, viscosity,
thermal conductivity, surface tension and gross heating value.
COMPUTER PREDICTION METHODS
Computer methods for predicting physical and themody-
namics properties for light hydrocarbons and natural gas con-
stituents are widely available. They are routinely used by
many involved in the design and operation of natural gas proc-
essing facilities. This section emphasizes hand calculation
methods that give reliable estimates of physical properties.
They should be used when a number is required quickly, for
an “order of magnitude” check when evaluating a more de-
tailed procedure, or when a computer is not available.
There will be presentation of some computer results. The
use of equations of state for property predictions is convenient
and easy, but they do not apply equally well for all properties.
Gas phase densities, volumes and compressibilities are pre-
dicted accurately and reliably. Liquid volumes and densities
are less accurate but still can be expected to generally be as
reliable as predictions by hand methods. Thermal conductivi-
ties, viscosities and surface tensions are not well predicted by
PVT equations of state. Computer programs cited or used are
selected examples of those widely available for prediction of
physical and thermodynamic properties. Inclusion here does
not represent GPA and/or GPSA endorsement of the pro-
gram(s). A good, reliable equation of state properly pro-
grammed and applied will always be the most convenient
method for obtaining engineering accuracy gas phase proper-
ties. Unfortunately, widespread availability and/or ease of use
are not suitable criteria for choice of an equation of state pro-
gram. The methods detailed here are for hand calculation of
physical properties.
COMPRESSIBILITY OF GASES
Pure Gases
When dealing with gases at very low pressure, the ideal gas
relationship is a convenient and generally satisfactory tool.
For measurements and calculations for gases at elevated pres-
sure, the use of the ideal gas relationship may lead to errors
as great as 500%, as compared to errors of 2 or 3% at atmos-
pheric pressure.
The many PVT equations of state that have been proposed
(see Section 25) for representing the pressure-volume-tem-
perature relationship of gases are complicated and require a
computer or programmable calculator to solve in a reasonable
length of time. A generalized corresponding states correlation
of compressibility factors is reasonably convenient and suffi-
ciently accurate for normal engineering requirements. The
procedure provides a correction factor, Z, by which the volume
computed from the ideal gas equation is converted to the cor-
rect volume for real gas.
PV = ZmRT /MW = ZnRT Eq 23-1
The compressibility factor Z is a dimensionless parameter
independent of the quantity of gas and determined by the
characteristics of the gas, the temperature, and pressure.
Once Z is known or determined, the calculation of pressure-
temperature-volume relationships may be made with as much
ease at high pressure as at low pressure.
The equation used to calculate gas density is:
MW • P
ρ = Eq 23-2
10.73 • T • Z
The value 10.73 for R is used when pressure is in psia, vol-
ume in cubic feet, quantity of gas in pound moles, and tem-
perature in °R. Values of R for other combinations of units are
given in Section 1.
According to the theorem of corresponding states, the devia-
tion of any actual gas from the ideal gas law is proportionally
the same for different gases when at the same corresponding
state. The same corresponding states presumably are found
at the same fraction of the absolute critical temperature and
pressure, which, for pure gases, are known as the “reduced
conditions.”

FIG. 23-3
Calculation of Pseudocritical Temperature and Pressure for a Natural Gas Mixture

Component Component Component Mixture

Mole Pseudocritical Pseudocritical
Critical Critical Molecular Molecular
Component Fraction, Temperature, Pressure,
Temperature, Pressure, Weight, Weight,
yi Tpc, °R Ppc, psia
Tci, °R Pci, psia MW yi • MW
CH4 0.8319 343.0 285.3 666.4 554.4 16.043 13.346
C2H6 0.0848 549.6 46.6 706.5 59.9 30.070 2.550
C3H8 0.0437 665.7 29.1 616.0 26.9 44.097 1.927
iC4H10 0.0076 734.1 5.58 527.9 4.01 58.123 0.442
nC4H10 0.0168 765.3 12.86 550.6 9.25 58.123 0.976
iC5H12 0.0057 828.8 4.72 490.4 2.80 72.150 0.411
nC5H12 0.0032 845.5 2.71 488.6 1.56 72.150 0.231
nC6H14 0.0063 913.3 5.75 436.9 2.75 86.177 0.543
Tpc = 392.62 Ppc = 661.57 MWm = 20.426
G = 20.426/28.9625 = 0.705

23-10
 Reduced Temperature, Tr = T/Tc Eq 23-3
Reduced Pressure, Pr = P/Pc Eq 23-4
For gas mixtures, the reduced conditions are determined us-
ing pseudocritical values instead of the true criticals:
Reduced Temperature, Tr = T/Σ(yiTc i) = T/Tpc Eq 23-3a
Reduced Pressure, Pr = P/Σ(yiPc i) = P/Ppc Eq 23-4a
Any units of temperature or pressure may be used provided
that the same absolute units be used for T as for Tc (Tpc) and
for P as for Pc (Ppc). The “average molecular weight” for a gas
mixture is defined the same way – MWavg = Σ(yi • MWi). Cal-
culation of pseudo criticals and MWavg for a typical natural gas
is illustrated in Fig. 23-3. Critical temperature and pressure
for the hexanes and heavier or heptanes and heavier fraction
can be estimated from molecular weight and specific gravity
or average boiling point and relative density using procedures
presented in this section.
Attempts to prepare a generalized plot suitable for applica-
tion to the low molecular mass hydrocarbons, including meth-
ane, ethane, and propane, indicate that an error frequently in
excess of 2 to 3% was unavoidable due to their departure from
the theorem of corresponding states. Fig. 23-4, prepared using
pure component and gas mixture data, can be used to estimate
Z (2-3% error) for pure hydrocarbon gases for this application.
Reduced temperature and pressure are used instead of
pseudoreduced values. At low pressures, the different com-
pounds appear to conform more closely. The compressibility
factor may be assumed equal to 1.0 at low pressure. Errors
generally will be 2-3% for pressures of 300 psia or less so long
as the gas is 50°F or more above its saturation temperature
at the pressure of concern.
P-H diagrams like those in Section 24, Thermodynamic
Properties, can be used to determine gas volumes, densities
and compressibilities for pure hydrocarbon and nonhydrocar-
bon vapors. Interpolation between specific volume curves on
a P-H diagram does not yield results of high accuracy. Pure
component PVT properties are more accurately obtained from
an equation of state, particularly if that equation has been
fitted to volumetric data for the specific component. Tabula-
tions of properties obtained in this way can be found in the
literature.12
Example 23-1 — Pure component properties
Using Fig. 24-26, the P-H diagram for propane, calculate the
density of propane vapor at 200°F and 100 psia.
Solution Steps
On the P-H diagram at the intersection of the T = 200°F,
P = 100 psia lines read v = 1.5 ft3/lb. Then:
ρ = 1/1.5 = 0.667 lb.f t3
Using the EZ*THERMO90 version of the SRK91 equation of
state, ρ is calculated to be 0.662 lb/ft3, from which
v = (1/0.662) = 1.51 ft3/lb.
For propane at 200°F and 100 psia using data from Fig.
24-26
(44.10) (100)
MW • P
Z = = = 0.936
R•T•ρ (10.73) (458.67 + 200) (0.667)
The SRK calculation gives ρ = 0.662 lb/ft3, and Z = 0.941.
23-11
Gas Mixtures
Additional information regarding the calculation of compressi-
bility factors for mixtures at pressures below 150 psia can be
obtained from GPA Standard 2172, “Calculation of Gross Heating
Value, Relative Density and Compressibility Factor for Natural
Gas Mixtures from Compositional Analysis”.
Minor Amounts of Nonhydrocarbons — Fig. 23-41
shows compressibility factors for typical sweet natural gases.
Use of compressibility factors from Fig. 23-4 should yield mix-
ture volumes (densities) within 2% to 3% of the true values
from a reduced temperature slightly greater than 1.0 to the
limits of the chart for both temperature and pressure. The
chart was prepared from data for binary mixtures of methane
with ethane, propane and butane and data for natural gases.
No mixtures having average molecular weights greater than
40 were used, and all gases contained less than 10% nitrogen
and less than 2% combined hydrogen sulfide and carbon diox-
ide. Fig. 23-4 is applicable for temperatures 20°F or more
above saturation and to pressures as high as 10,000 psia.
Appreciable Amount of Nonhydrocarbons —
Fig. 23-4 does not apply for gases or vapors with more than
2% H2S and/or CO2 or more than 20% nitrogen. For gas or
vapors that have compositions atypical of natural gases, or for
mixtures containing significant amounts of water and/or acid
gases, and for all mixtures as saturated fluids, other methods
should be employed.
Reasonably accurate gas compressibility factors for natural
gases with high nitrogen content, up to 50% nitrogen or even
higher, can be obtained using Fig. 23-4, if the molar average
pseudocriticals from Eqs 23-3a and 23-4a are employed. This
same approach is recommended for gas condensate fluids con-
taining appreciable amounts of heptanes and heavier compo-
nents. Critical temperature and pressure for the heptane and
heavier fraction or fractions can be estimated from molecular
mass and relative density, or average boiling point and rela-
tive density, using correlations presented in this section.
Figs. 23-5, 23-6 and 23-7 provide compressibility factors for
low molecular weight natural gases. These figures cover a
wide range of molecular weights (15.95 to 26.10), tempera-
tures (–100 to 1000°F) and pressures (up to 5,000 psia). For
gases with molecular masses between the molecular masses
shown in Figs. 23-5 through 23-7, linear interpolation between
adjacent charts should be used to compute the compressibility.
In general, compressibilities for gases with less than 5%
noncondensable nonhydrocarbons, such as nitrogen, carbon
dioxide, and hydrogen sulfide, are predicted with less than 2%
error. When molecular weight is above 20 and compressibility
is below 0.6, errors as large as 10% may occur.
Effect of Acid Gas Content — Natural gases which
contain H2S and/or CO2 exhibit different compressibility fac-
tor behavior than do sweet gases. Wichert and Aziz3 present a
calculational procedure to account for these differences. The
method uses the standard gas compressibility factor chart
(Fig. 23-3) and provides accurate sour gas compressibilities for
gas compositions that contain as much as 85% total acid gas.
Wichert and Aziz define a “critical temperature adjustment
factor,” ε, that is a function of the concentrations of CO2 and
H2S in the sour gas. This correction factor is used to adjust the
pseudocritical temperature and pressure of the sour gases ac-
cording to the equations:
Tc′ = Tc − ε Eq 23-5
 FIG. 23-4
Compressibility Factors for Natural Gas1

23-12
 FIG. 23-5
Compressibility of Low-Molecular-Weight Natural Gases11

23-13
 FIG. 23-6
Compressibility of Low-Molecular-Weight Natural Gases11

23-14
 FIG. 23-7
Compressibility of Low-Molecular-Weight Natural Gases11

23-15
 FIG. 23-8
Pseudocritical Temperature Adjustment Factor3, ε, °F

Pc Tc′ The pseudocritical temperature adjustment factor is read

Pc′ = Eq 23-6 from Fig. 23-8 to be 29.8°F. The adjusted pseudocritical tem-
Tc + B′ (1 − B′)ε
perature is:
The pseudocritical temperature adjustment factor is plotted
in Fig. 23-8. To use the factor, the pseudocritical temperature Tc′ = 433.9 − 29.8 = 404.1 °R
and pressure are calculated following the procedure outlined
earlier. In this calculation, the H2S and CO2 are included as The adjusted pseudocritical pressure is:
well as hydrocarbon and other nonhydrocarbon constituents.
(826.9) (404.1)
The pseudocritical temperature adjustment factor is read Pc′ = = 761.7 psia
from Fig. 23-8, and used to adjust the values of critical tem- 433.9 + 0.2 (1 − 0.2) 29.8
perature and pressure. The reduced temperature and reduced
pressure are calculated using the adjusted values. The com- The pseudocritical temperature and pseudoreduced
pressibility factor is then read from Fig. 23-4. pressure are:
Example 23-2 — A sour natural gas has the composition 100 + 459.67 1000
shown below. Determine the compressibility factor for the gas Tr = = 1.385 Pr = = 1.313
404.1 761.7
at 100°F and 1000 psia.
Z = 0.831 (Fig. 23-4)
Solution Steps
90
The first step is to calculate the pseudocritical temperature (The EZ*THERMO version of the SRK gives Z = 0.838.)
and pseudocritical pressure for the sour gas.
Pseudo- Pseudo-
Mole critical critical HYDROCARBON FLUID DENSITIES
Comp. Fraction Tc, °R Tc, °R Pc, psia Pc, psia
CO2 0.10 547.6 54.8 1071 107.1
H2S 0.20 672.1 134.4 1300 260.0 Data and Correlations
N2 0.05 227.2 11.4 493.1 24.7 Fig. 23-9 presents saturated fluid densities (liquid and va-
CH4 0.60 343.0 205.8 666.4 399.8 por) for hydrocarbons and liquid densities for some mixtures.
C2H6 0.05 549.6 27.5 706.5 35.3 Fig. 23-10 is a plot of relative density as a function of tempera-
433.9 826.9 ture for petroleum fractions.

23-16
 FIG. 23-9
Hydrocarbon Fluid Densities2, 3, 19

23-17
 FIG. 23-10
Approximate Specific Gravity of Petroleum Fractions

23-18
 FIG. 23-11
Effect of Temperature on Hydrocarbon Liquid Densities19

23-19
 FIG. 23-12
Specific Gravity of Petroleum Fractions

23-20
 FIG. 23-13
Specific Gravity of Paraffinic Hydrocarbon Mixtures

23-21
 Subcooled liquid hydrocarbon densities from –50°F to
+140°F are shown on Fig. 23-11. Corrections to liquid hydro-
carbon densities due to high pressure are shown on Fig. 23-15.
Specific gravities of petroleum fractions are given in Fig.
23-12 where temperature ranges from 0° to 1000°F and pres-
sures from atmospheric to 1500 psia. The petroleum fraction
is identified within the center grid by two of three charac-
teristics — API gravity at 60°F, the Watson characterization
factor, Kw, or the mean-average boiling point. The mean-av-
erage boiling point can be determined from Fig. 23-18 together
with the API gravity and an ASTM D-86 distillation of the
petroleum fraction. The characterization factor, Kw, is defined
in the inset example shown to illustrate use of Fig. 23-12.
The specific gravity of paraffinic hydrocarbons at their boil-
ing point or bubble point pressure and temperature can be
obtained from Fig. 23-13. The nomograph applies to mixtures
as well as to single components. Alignment points for paraf-
finic mixtures and pure components are located according to
molecular weight.
Fig. 23-13 generally predicts specific gravities within 3% of
measured values for paraffinic mixtures. However, the accu-
racy is somewhat less for mixtures having:
• Reduced temperatures above 0.9.
• Molecular weights less than 30 (low temperature region)
and where methane is a significant part of the liquid.
Density of Saturated and Subcooled Liquid Mix-
tures — A versatile, manual procedure for calculating the
density of gas-saturated and subcooled hydrocarbon liquid
mixtures was presented by Standing and Katz.1 The basic
method proposed uses the additive volume approach for pro-
pane and heavier components at standard conditions, then
corrected this ideal volume using apparent densities for the
gaseous components ethane and methane. The resulting
pseudodensity at 60°F and 14.7 psia is corrected for pressure
using a hydrocarbon liquid compressibility chart, then for tem-
perature using a thermal expansion chart (Fig. 23-17) for hy-
drocarbon liquids. Experience with crude oils and rich
absorber oils shows this correlation will predict densities
within 1 to 4% of experimental data.
The original correlation did not have a procedure for han-
dling significant amounts of nonhydrocarbons and had a fairly
narrow temperature range of 60°F to 240°F. The following pro-
cedures and charts are recommended for general applicability
to liquids containing components heavier than pentanes (gas
saturated or subcooled) at pressures up to 10,000 psia and
temperatures from –100°F to 600°F. Significant amounts of
nonhydrocarbons can be handled by this procedure (up to
20% N2, 80% CO2, and 30% H2S).
1. Set up a calculation table as shown in the example in Fig.
23-16.
2. Calculate the density of propane and heavier (C3 plus)
or, if H2S is present, of H2S and heavier (H2S plus) com-
ponents, assuming additive volumes.
Densityof C3 plus (or H2S plus)
Weight C3 plus (or H2S plus) c o mpo nents
= Eq 23-7
Vo l C3 plus (o r H2S plus) components
3. Determine the weight percent of (N2 + C2) in the (N2 + C2
plus) fraction.
Wt (N2 + C2)
Wt % (N2 + C2) = • 100 Eq 23-8
Wt (N2 + C2 plus)
23-22
4. Use Fig. 23-14 to determine the pseudodensity of the
(N2 + C2 plus) fraction. Enter with the C3 plus (or H2S
plus) density from Step 2 in the upper left of the chart
and go horizontally to the line (interpolate if necessary)
representing the weight % (N2 + C2) , then look up and
read the pseudodensity of the (N2 + C2 plus) along the top
of the chart.
At temperatures below –20°F, ethane can be included in
Step 2 and only N2 used in Steps 3 and 4.
5. If CO2 is not present, go to Step 6. If it is present, then
account for it on an additive volume basis as shown.
Densityof CO2 and (N2 + C2 plus)
Wt CO2 + Wt (N2 + C2 plus)
= Eq 23-9
Vol CO2 + Vol (N2 + C2 plus)
where
Wt (N2 + C2 plus)
Vol (N2 + C2 plus) =
Density (N2 + C2 plus)
6. Calculate the weight percent methane
Wt % methane =
Wt methane
• 100 Eq 23-10
total Wt
7. Enter the top of Fig. 23-14 with the pseudodensity from
Step 4 or 5 as appropriate, and drop vertically to the line
(interpolation may be required) representing the weight
percent methane. Read the pseudodensity of the mixture
(60°F and 14.7 psia) on the right side of the chart.
8. Correct the pseudodensity to the actual pressure using
Fig. 23-15. Add the correction to the pseudodensity from
Step 7.
9. Correct the density at 60°F and pressure to the actual
temperature using Fig. 23-17. Add the correction to the
density from Step 8.
This procedure should not be used in the critical region. Mix-
tures at temperatures greater than 150°F which contain more
than 60 mole percent methane or more than 80 mole percent
CO2 have been demonstrated to be problem areas. Away from
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 plus with relatively small amounts of dissolved gaseous
components (errors are usually less than 3%). Note that den-
sities of C2 plus, C3 plus, CO2 plus, or C4 plus 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 plus 44.836 lb
Density of C3 plus = =
Vo l o f C3 plus 1.0128 ft3
= 44.275 lb/ft3
 0.567 
Wt % C2 in C2 plus = 
0.567 + 44.836  • 100 = 1.25%
 
Density of C2 plus from Fig. 23-14 = 44.0 lb/ft3
45.403 + 17.485
Density of CO2 plus = = 45.75 lb/ft3
 45.403 
 44.0  + 0.3427
 
 FIG. 23-14
Pseudo Liquid Density of Systems Containing Methane and Ethane

23-23
 FIG. 23-15
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
Total 1.00000 66.240

3.352
Wt % CH4 in Total = • 100 = 5.1%
66.241
FIG. 23-16
Pseudodensity of mixture at 60°F and 14.7 psia from
Density Correction for Compressibility of Fig. 23-14 = 42.9 lb/cu ft
Hydrocarbon Liquids
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

(Density by EZ*THERMO version of SRK using Costald92
41.815 lb/ft3.
Experimental density35 at 120°F and 1760 psia = 41.2 lb/ft3
Error = (41.8 − 41.2)/41.2 = 0.015, or 1.5%

BOILING POINTS, CRITICAL

PROPERTIES, ACENTRIC FACTOR,
VAPOR PRESSURE
Boiling Points
Fig. 23-18 shows the interconversion between ASTM D-86
distillation 10% to 90% slope and the different boiling points
used in characterizing fractions of crude oil to determine the
properties; VABP, WABP, CABP, MeABP, and MABP. On the
basis of ASTM D-86 distillation data, the volumetric average
boiling (VABP) point is defined as:
VABP = (t10 + t30 + t50 + t70 + t90)/5 Eq 23-11
Where the subscripts 10, 30, 50, 70, and 90 refer to the vol-
ume percent recovered during the distillation. The 10% to 90%
slope used as the abscissa in Fig. 23-18 is defined as:
slope = (t90 − t10)/(90 − 10) Eq 23-12
To use the graph, locate the curve for the distillation VABP
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.

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

23-25
Example 23-4 — Determine the mean average boiling point The significance of the various average boiling points, inter-
(MeABP) and the molecular weight for a 56.8° API petroleum conversion of D-86 and D-1160 ASTM distillations, and the
fraction with the following ASTM distillation data. calculation of true-boiling point and atmospheric flash curves
from ASTM distillation data can be found in Chapters 3 and
% Over Temperature, °F 4 of the API Technical Data Book.36
IBP 100
Molecular weight can be calculated from Eq 23-13 using Me-
5 130 ABP in °R and S (specific gravity at 60°F) .
10 153
20 191 (
MW = 204.38 [(T)0.118] (S1.88) e(0.00218 T − 3.075 S)) Eq 23-13
30 217 This relationship has been evaluated in the molecular
40 244 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 was about
50 280 7%. Eq. 23-13 is best used for molecular weights above 115,
60 319 since it tends to over-predict below this value.
70 384 Example 23-5 — Calculation of molecular weight.
80 464
From Example 23-4:
90 592
EP 640 S = 0.7515 fo r 56.8° API
MeABP = 271 + 460 = 731°R
IBP = initial boiling point EP = end po int
Using Eq 23-13,
Slope = (592 − 153)/80 = 5.49
MW = 204.38[(731)0.118][(0.7515)1.88 ]
VABP = (153 + 217 + 280 + 384 + 592)/5 = 325°F
731) − (3.075 • 0.7515)
Refer to Fig. 23-18. Read down from a slope of 5.49 to the
[e(0.00218 •
] = 127.0
interpolated curve for 325°F in the set drawn with dashed Critical Properties
lines (MeABP). Read a correlation value of –54 on the ordinate.
Then: Critical properties are of interest because they are com-
monly used to find reduced conditions of temperature and
MeABP = 325 − 54 = 271°F pressure which are required for corresponding states correla-

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

23-26
 FIG. 23-19
Low-Temperature Vapor Pressures for Light Hydrocarbons

23-27
 FIG. 23-20
High-Temperature Vapor Pressures for Light Hydrocarbons

23-28
 FIG. 23-21
Viscosities of Hydrocarbon Liquids

23-29
tions. Pseudocriticals are used in many corresponding states Use Eq 23-15 to calculate the pseudocritical temperature as:
correlations for mixtures.
Tpc = 24.2787 (271 + 460)0.58848 (0.7515)0.3596
The following equations taken from the API Technical Data
Book36a, b can be used to estimate pseudo critical temperature = 1062°R or 602°F
and pressure for petroleum fractions (pseudo, or undefined
components): Fo r this 56.8°API fluid,estimate the pseudo c ritic al pres-
sure, using Eq 23-14 and MeABP = 271°F:
Ppc = [ 3.12281 (109) T −2.3125] • S 2.3201 Eq 23-14
Ppc = [ 3.12281 (109)] (271 + 460)−2.3125 (0.7515)2.3021
Tpc = 24.2787 • T 0.58848
•
0.3596
S Eq 23-15
= 386 psia
These equations are in terms of T = MeABP (°R) and specific
gravity (S) at 60°F. Both of these correlations have been evalu- Acentric Factor
ated over the range of 80 to 690 molecular weight; 70 to 295°F
normal boiling point; and 6.6° to 95° API. The acentric factor, ω, is frequently used as a third parame-
Example 23-6 — Pseudocritical temperature and pressure. ter in corresponding states correlations. It is tabulated for
pure hydrocarbons in Fig. 23-2. Note that the acentric factor
Take the previous mixture (from Example 23-4) with: is a function of Pvp, Pc, and Tc.
VABP = 325°F
MeABP = 271°F It is arbitrarily defined by
API = 56.8° ω = −log (Pvp/Pc) Tr = 0.7 − 1.0 Eq 23-16
Molecular Weight = 127 (Ex. 23-5) This definition requires knowledge of the critical (pseudo-
ASTM D-86, 10% to 90% Slope = 5.49 critical) temperature, vapor pressure, and critical (pseudo-
Find its pseudocritical temperature. critical) pressure.
Solution Steps For a hydrocarbon mixture of known composition, and con-
From Fig. 23-18 with ASTM D-86 slope = 5.49 find a VABP taining similar components, the acentric factor may be esti-
correction of about –85°F (extrapolated from the left-hand mated, with reasonable accuracy, as the molar average of the
group). individual pure component acentric factors:
MABP = 325 − 85 = 240°F ω = Σ xi ωi Eq 23-17

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

23-30
 FIG. 23-23
Hydrocarbon Gas Viscosity

23-31
 If the vapor pressure is not known, ω can be estimated38 for Ppc = 356 psia
pure hydrocarbons or fractions with boiling point ranges of From Eq. 23-15, the pseudocritical temperature is:
50°F or less, using Eq. 23-18.
Tpc = 24.2787 • (875)0.58848 • (0.871)0.3596
 3   log Pc − log 14.7 
ω =    − 1.0 Eq 23-18
7    Tc   Tpc = 1244°R
 T  − 1 
  b   3  lo g (356) − log (14.7) 
ω =    − 1.0 = 0.447
7    1244  
Example 23-7 — Acentric factor.   875  − 1.0 
   
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. Vapor Pressure
In order to use Eq 23-18 we need the average boiling point The vapor pressures of light hydrocarbons and some com-
(MeABP); the pseudocritical temperature (a function of mon inorganics in the temperature range below 100°F are
MABP); and the pseudocritical pressure (a function of Me- given in Fig. 23-19. Vapor pressures at higher temperatures,
ABP). up to 600°F, are given in Fig. 23-20 for the same compounds.
Note that, except for ethylene and propylene, the hydrocar-
From Fig. 23-18, the correction to VABP for mean average bons are all normal paraffins.
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. 23-14, the pseudocritical pressure is: VISCOSITY
T = 415 + 460 = 875°R Figs. 23-21 through 23-29 give the viscosity of hydrocarbon
liquids and vapors, water, steam, and miscellaneous gases. Fig.
S for 41°API = 141.5/(131.5 + 41) = 0.871 23-21 gives data on hydrocarbon liquids. Figs. 23-22, 23-23 and
23-24 present data on hydrocarbon gases. To correct for pressure,
Ppc = [ 3.12281 109 (875)−2.3125] • (0.871)2.3201 the gas viscosity from Fig. 23-22 is adjusted from atmospheric

FIG. 23-24
Viscosity Ratio vs. Pseudoreduced Temperature

23-32
 FIG. 23-25 FIG. 23-26
Viscosity of Miscellaneous Gases – One Atmosphere Viscosity of Air43, 44, 45

pressure values by Figs. 23-23 and 23-24. Fig. 23-24 is pre- Hence, the viscosity at 1000 psia and 100°F is:
ferred when the reduced temperature is greater than 1.0. Fig.
23-28 gives the viscosity of hydrocarbon liquids containing dis- µ = (1.21) (0.0105) = 0.0127 centipoise
solved gases. Note that Fig. 1-7 gives conversion factors for The viscosity of a gaseous mixture with large amounts of
viscosity. nonhydrocarbons is best determined by using the method
of Dean and Stiel.41 This method is particularly useful for
Calculation of Gas Mixture Viscosity handling natural gas with high CO2 content. Tested against
Example 23-8—Determine the viscosity of a gas of molecular 30 CO2-N2 mixtures, it had an average deviation of 1.21%
weight 22 at 1,000 psia and 100°F. Tc = 409°R, Pc = 665 psia at pressures up to 3525 psia. It makes use of a factor, ξ,
defined as:
Solution Steps 1/6
 (Tcm) 
= 22/28.964 = 0.760 ξ = 5.4402  
id
G 2/3  Eq 23-19
 
From Fig. 23-23 at 100°F:  ( Σ (xi MW i) ( Pcm )) 

µA = 0.0105 centipoise If the reduced temperature Tr is > 1.5, then

ξ µ A = [166.8 (10−5)] [(166.8 • 10−5)(0.1338 Tr − 0.0932)5/9]

Then:
100 + 460 1000
Tr = = 1.37 Pr = = 1.50 Eq 23-20
409 665
Note: Pseudocritical temperature and pressure should be If Tr is ≤ 1.5,
calculated as outlined in this section, if the composition of the
gas is available. ξ µA = 34.0 10−5 (Tr 8/9 ) Eq 23-21
 
Because Tr > 1.0, Fig. 23-24 is preferred to obtain the cor- In either case, µA is found by dividing (ξ µA) by ξ.
rection for elevated pressure to the viscosity at one atmos-
phere. Equations 23-19 through 23-21 will predict the viscosity of pure
gases as well as mixtures. To apply the Dean and Stiel41 method
From Fig. 23-24: to mixtures, the pseudocritical volumes, compressibilities, and
µ temperatures are calculated by the Prausnitz and Gunn42 mixing
= 1.21 rules:
µA

23-33
 Vcm = Σ (yi Vc i) Eq 23-22 B = 1105.7
Zcm = Σ (yi Zci) Eq 23-23 11.99
A =  101.78 (325 + 459.67) − 0.175− 29.263 = 0.02645
Tcm = Σ (yi Tci) Eq 23-24   1105.3

Zcm R Tcm The same constants are employed at 100°F and at 210°F.
Pcm = Eq 23-25 1.8 (1105.7)
Vcm
η = 0.02645 • e 559.67 = 0.926 cs at 100°F
Example 23-9 — For a temperature of 50°F and a pressure of
300 psia, estimate the viscosity of a mixture of 80 mole percent 1.8 (1105.7)
methane, 15 mole percent nitrogen, and 5 mole percent carbon η = 0.02645 • e 669.67
= 0.517 cs at 210°F
dioxide. Calculations are summarized in Fig. 23-30:
The reported values are 0.93 and 0.52 centistokes, respec-
Zcm R Tcm tively.
Pcm =
Vcm
(0.2875) (10.73) (335.9)
= = 663.4 psia THERMAL CONDUCTIVITY
1.562
Substituting from the calculation table in Fig. 23-30 into Thermal conductivity for natural gas mixtures at elevated
Eq 23-19: pressure can be calculated from an atmospheric value and a
(5.4402) (335.9)1/6 pressure correction. Figs. 23-31 through 23-36 present low
ξ = = 0.043 pressure thermal conductivity data of gases developed from
(19.237)1/2 (663.4)2/3 published data.51, 54 The pressure correction of Lenoir et al.52
T 509.7 shown in Fig. 23-32 is applied to these low pressure data as
Tr = = = 1.517 illustrated below. The thermal conductivity of liquid paraffin
Tcm 335.9
hydrocarbons is plotted in Fig. 23-35 and the thermal conduc-
Because Tr > 1.5, the expression to be used for ξµA is Eq 23- tivity of liquid petroleum fractions in Fig. 23-36.
20.
ξ µA = 166.8 (10−5) [0.1338 Tr − 0.0932]5/9
FIG. 23-27
= 166.8 (10−5) [(0.1338) (1.517) − 0.0932]5/9
Water Viscosity at Saturated Conditions
ξ µA = 48.91 (10−5)
µA = 0.01138 centipoise
Using Fig. 23-23 and correcting for the nitrogen and carbon
dioxide content of this mixture gives a µA of 0.0116 cp. This is a
good check. Had a 20% N2 content been chosen for this example,
the N2 range of Fig. 23-23 would have been exceeded and use of
the Dean and Stiel method would have been required. When the
conditions at hand 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 using the equations
given below 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 • e1.8 B / T Eq 23-26
Kw
A = (101.78 Tb− 0.175 − 29.263) Eq 23-27
B
ln (B) = 4.717 + 0.00292 Tb Eq 23-28
Example 23-10 — At 100°F and 210°F find the viscosity of a
heavy condensate having a mid-boiling 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

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 k/kA = 1.15
46, 47
Viscosity of Steam
k = (1.15) (0.0248) = 0.0285 Btu/[(hr • sq ft • °F)/ft]
Another method for estimating thermal conductivity is pre-
sented by Stiel and Thodos.53
To determine the thermal conductivity of a gaseous mixture
of defined components, the thermal conductivity of each com-
ponent at the given temperature is read from the charts pro-
vided and the thermal conductivity of the mixture is
determined by the “cube root rule”.56 This rule is applicable
to mixtures of simple gases; it does not apply to mixtures con-
taining CO2 because the thermal conductivity goes through a
maximum.

Σ (yi ki √  i)
3

MW
km = 3 Eq 23-29
Σ yi √

MW i
The cube root rule was tested56 against 17 systems with an
average deviation of 2.7%.
The thermal conductivity of a liquid mixture is best deter-
mined by the method of Li,55 based on volume fractions.
Example 23-12 — Find the thermal conductivity of the
gaseous mixture shown in Fig. 23-37 at 200°F and one at-
mosphere.

0.05774
km = = 0.0205 Btu/[(hr • sq ft • °F)/ft]
2.822

TRANSPORT PROPERTY REFERENCES

There are no simple correlations for the transport properties
of viscosity and thermal conductivity, as evident from the pre-
ceding paragraphs. For pure components, the best approach
is a complicated equation with many constants that must be
fitted to experimental data, or extensive tables. Vargaftik62
and Touloukian65 each have extensive collections of experi-
mental data.

Example 23-11 — Find the thermal conductivity of a 25 mo-

lecular weight natural gas at 700 psia and 300°F. Tc = 440°R, SURFACE TENSION
Pc = 660 psia
Solution Steps The interior molecules of a liquid exert upon the surface
molecules an inward force of attraction which tends to mini-
From Fig. 23-31, at 300°F: mize the surface area of the liquid. The work required to en-
large the surface area by one square centimeter is called the
kA = 0.0248 Btu/[(hr • sq ft • °F)/ft] surface free energy. The perpendicular force in the liquid sur-
face, called surface tension, exerts a force parallel to the plane
Tr = (300 + 460)/440 = 1.73
of the surface. Surface tension, an important property where
Pr = 700/660 = 1.06 wetting, foaming, emulsification, and droplet formation are
encountered, is used in the design of fractionators, absorbers,
From Fig. 23-32: two-phase pipelines, and in reservoir calculations.

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

Mole Molecular VC, PcVc

Tc, °R Pc, psia Zc = Vcm = ΣyiVci Tcm = ΣyiTci MWm = ΣyiMWi
Fraction Weight cu ft/lb mole 10.73 Tc
CH4 0.80 16.043 343.0 666.4 1.59 0.2879 1.272 274.4 12.834
N2 0.15 28.013 227.2 493.1 1.43 0.2892 0.215 34.1 4.202
CO2 0.05 44.010 547.6 1071. 1.51 0.2752 0.076 27.4 2.201
Mixture 1.00 – – 1.562 0.2875 1.562 335.9 19.237

23-36
 FIG. 23-31
Thermal Conductivity of Natural and Hydrocarbon Gases
at One Atmosphere (14.696 psia)
Pure Components
The surface tension of pure hydrocarbons as a function of
temperature may be obtained from Fig. 23-38.
Mixtures
Surface tension for binaries of known composition at or near
atmospheric pressure may be calculated78 using:
σ1 • σ2
σm = Eq 23-30
σ1 • x2 + σ2 • x1
The presence of inert gases, such as N2 and CO2, in the liquid
phase tends to lower the surface tension of the liquid. Where
the concentration of inert gases in the liquid exceeds 1.0 mole
%, estimated values of surface tension may be 5 to 20% higher
than actual values for the mixture.
GROSS HEATING VALUE OF NATURAL
GASES
The gross heating value, specific gravity, and compressibil-
ity of a natural gas mixture may be calculated when a complete
compositional analysis of the mixture is available.
Gross Heating Value — is defined as 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 value can be calculated per
unit volume of an ideal gas, or per unit volume of a real gas as
follows:
Hv = Σ (yiHvi) Eq 23-31
23-37
FIG. 23-32
Thermal Conductivity Ratio for Gases
Values for Hv and MWi are obtained from Fig. 23-2.
To calculate the ideal gross heating value produced or used
for a given period of time, Hv must be multiplied by the ideal
gas volumetric flow rate of gas for the time period. To employ
a real gas flow to calculate the ideal gross heating value pro-
duced or used for a given period of time, the real gas flow rate
must be converted to the ideal gas flow rate by dividing by the
compressibility factor. Often the heating value Hv is divided
by the compressibility factor in preparation for multiplying by
the real gas flow rate. Thus Hv/Z is gross heating value per
unit volume of real gas.
Specific gravity (also termed relative density or gas
gravity) — is defined as the ratio of gas density (at the tem-
perature and pressure of the gas) to the density of dry air (at
the air temperature and pressure).
ρ MW P Ta Za
G = = Eq 23-32
ρs MWa Pa Z
The ideal gas specific gravity is the ratio of the molecular
weight of the gas to the molecular weight of dry air.
MW
Gid = Eq 23-33
MWa
For a mixture
G id = Σ (yi Giid) Eq 23-34
The specific gravity G is measured and is generally used to
calculate the molecular weight ratio Gid when the gas compo-
sition is not available.
 FIG. 23-33 FIG. 23-34
Thermal Conductivity of Miscellaneous Gases Thermal Conductivity of Hydrocarbon Gases
at One Atmosphere59, 60, 61, 62 at One Atmosphere67, 68, 69

MW G (Pa T Z) When the gas is wet but not water saturated and the com-
G id = = Eq 23-35 ponent analysis is on a dry basis, it is necessary to determine
MWa P Ta Z
the water content and to adjust the mole fractions to reflect
the presence of water. When the water mole fraction, yw, is
The temperatures and pressures used must correspond to known, the adjusted mole fractions can be obtained from
actual measurement conditions or serious errors in Gid can Eq 23-37.
occur.
The yiw values are used in the gross heating value and gas
Corrections for Water Content — When the gas is compressibility calculations after adding water to the compo-
water saturated but the component analysis is on a dry basis, nent list. If the dry gross heating value is known, the effect of
the component analysis must be adjusted to reflect the pres- the water content can be calculated using:
ence of water. The mole fraction of water in the mixture is
estimated as: Hv (wet) = (1 − yw) Hv (dry) + 50.3 yw Eq 23-38

Pow nw Calculations — Additional details on these calculational

yw = = (on a one mole basis) methods and examples are given in GPA Standard 2172, “Cal-
p (1 + nw) culation of Gross Heating Value, Relative Density and Com-
The adjusted mole fractions are calculated using the follow- pressibility Factor for Natural Gas Mixtures from
ing equation: Compositional Analysis”. A listing of the Basic source code for
a computer program to perform the calculations is given in
  Pow  2172.
i = yi 1 − 
yw  = yi (1 − yw) Eq 23-36
  P 
REFERENCES
For water saturated gas, water is added to the component
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i values are used in the gross heating value and 1. Standing, M. B. and Katz, D. L., Trans. AIME 146, 159 (1942).
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  1.7051   1.7051 • 29.94 4. Hall, K. R. and Yarborough, L., Oil Gas J. 71, No. 25, 82 (June 18,
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  P   P 
5. Hall, K. R. and Yarborough, L., Oil Gas J. 72, No. 7, 86 (Feb. 18,
Eq 23-37 1974).

23-38
 FIG. 23-35
Thermal Conductivity of Liquid Paraffin Hydrocarbons

FIG. 23-36
Thermal Conductivity of Liquid Petroleum Fractions58

23-39
 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
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