SECTION 23

Physical Properties
This section contains a number of charts, correlations, and
procedures for the prediction of physical properties of hydrocarbons and components found with them. Fig. 23-1 lists the
nomenclature used in this section.

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. 23-2 is a table containing frequently used physical properties for a number of hydrocarbons and other selected com-

FIG. 23-1
Nomenclature
B = second virial coefficient for a gas mixture,
(psia)-1
B = mole fraction H2S in sour gas stream, Eq 23-6
Bii = second virial coefficient for component i
Bij = second cross virial coefficient for components i
and j
bi1/2 = summation factor for component i
CABP = cubic average boiling point, F
d = density, g/cc
G = specific gravity or relative density (gas density)
Gi = specific gravity (gas gravity) of ideal gas, MW/MWa
Gid
= molecular weight ratio of component i in mixture
i
Hv = gross heating value per unit volume of ideal gas,
Btu/cu ft
Kw = Watson characterization factor, Fig. 23-12
k = thermal conductivity, Btu/[(hr sq ft F)/ft]
ka = thermal conductivity at one atmosphere,
Btu/[(hr sq ft F)/ft]
M = mass fraction
m = mass, lb
MW = molecular weight, lb/lb mole
MABP = molal average boiling point, F or R
MeABP = Mean average boiling point, F or R
n = number of moles, (mass/Mole weight)
P = pressure, psia
Pc = pseudocritical pressure adjusted for acid gas
composition, psia
Pvp = vapor pressure at a reduced temperature of 0.7
Pwo = vapor pressure of water, 0.25636 psia at 60F
R = gas constant, 10.73 (psia cu ft)/(R lb mole) for
all gases (see Section 1 for R in other units)
S = specific gravity at 60/60F
T = absolute temperature, R
t = ASTM D-86 distillation temperature for a given
volumetric fraction, F or R, Eq 23-11
Tc = pseudocritical temperature adjusted for acid gas
composition, R
V = volume, cu ft
VABP = volumetric average boiling point, F

23-1

W = mass, lb
WABP = weight average boiling point, F
yi = mole fraction of component i from analysis on dry
basis, Eq 23-37
x = mole fraction in liquid phase
yw
i = mole fraction of component i adjusted for water
content
y = mole fraction in gas phase
Z = compressibility factor
Greek
= pseudocritical temperature adjustment factor,
Eq 23-6
= MeABP/T pc
= density, lb/cu ft
= viscosity at operating temperature and pressure,
centipoise
A = viscosity at 14.7 psia (1 atm) and operating
temperature, centipoise
= factor defined by Eq 23-20
= surface tension, dynes/cm
= acentric factor
= kinematic viscosity, centistokes
Subscripts
a = air
b = boiling
c = critical
i = component i
L = liquid
m = mixture
pc = pseudocritical
r = reduced state
V = vapor
v = volume
w = water
Superscripts
id = ideal gas
w = water
o = reference state

FIG. 23-2
Physical Constants

23-2

FIG. 23-2 (Contd)

Physical Constants

23-3

FIG. 23-2 (Contd)

Physical Constants

23-4

FIG. 23-2 (Contd)

Notes and References for the Table of Physical Constants

23-5

FIG. 23-2 (Contd)

Notes and References for the Table of Physical Constants

23-6

FIG. 23-2 (Contd)

Notes and References for the Table of Physical Constants

23-7

FIG. 23-2 (Contd)

Notes for the Table of Physical Constants
a.
b.
c.
d.
e.

f.
g.
h.
i.
j.
k.
m.
n.
A.

B.
C.
D.

E.
F.
G.
H.
I.

Values in parentheses are estimated values.

The temperature is above the critical point.
At saturation pressure (triple point).
Sublimation point.
The + sign and number following specify the number of cm3 of
TEL added per gallon to achieve the ASTM octane number of
100, which corresponds to that of Isooctane (2,2,4Trimethylpentane).
These compounds form a glass.
Average value from octane numbers of more than one sample.
Saturation pressure and 60F.
Index of refraction of the gas.
Densities of the liquid at the normal boiling point.
Heat of sublimation.
Equation 2 of the reference was refitted to give:
a = 0.7872957; b = 0.1294083; c = 0.03439519.
Normal hydrogen (25% para, 75% ortho).

p.

An extrapolated value.

q.

Gas at 60F and the liquid at the normal boiling point.

r.

Fixed points on the 1968 International Practical Temperature

Scale (IPTS-68).

s.

Fixed points on the 1990 International Temperature Scale

(ITS-90).

t.

Densities at the normal boiling point are: Ethane, 4.540 [29];

Propane, 4.484 [28]; Propene, 5.083 [5]; Hydrogen Chloride,
9.948 [43]; Hydrogen Sulfide, 7.919 [25]; Ammonia, 5.688 [43];
Sulfur Dioxide, 12.20 [43].

u.

Technically, water has a heating value in two cases: net (1060.

Btu/lb) when water is liquid in the reactants, and gross
(+50.313 Btu/ft3) when water is gas in the reactants. The value
is the ideal heat of vaporization (enthalpy of the ideal gas less
the enthalpy of the saturated liquid at the vapor pressure).
This is a matter of definition; water does not burn.

v.

Extreme values of those reported by reference 19.

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.
Boiling point: the temperature at equilibrium between the liquid and vapor phases at 14.696 psia.
Freezing point: the temperature at equilibrium between the crystalline phase and the air saturated liquid at 14.696 psia.
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).

J.

The liquid value is not rigorously CP, but rather it is the heat capacity 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 60F 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 reaction 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.

The relative density (specific gravity): (liquid, 60F)/(water,

60F). The density of water at 60F is 8.3372 lb/gal.
The temperature coefficient of density is related to the expansion coefficient by: (/T)P/ = (V/T)P/V, in units of 1/T.
Pitzer acentric factor: = log10(P/Pc) 1, P at T = 0.7 Tc
Compressibility factor of the real gas, Z = PV/RT, is calculated
using the second virial coefficient.
The density of an ideal gas relative to air is calculated by dividing the molar mass of the of the gas by 28.9625, the calculated 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).

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
energy: British thermal unit (I.T.)
Btu = 251.9958 cal (I.T.) = 1055.056 J
Gas constant, R:
1.985887 Btu (I.T.)/(R lb mol)
10.73164 ft3 psia/(R lb mol)
8.314510 J/(K(mol)
Conversion factors:
1 ft3 = 7.480520 gal.
1 lbm/ft3 = 0.1336806 lbm/gal = 16.018462 kg/m3
1 psia = 0.06804596 atm = 6.894757 kPa
1 atm = 14.69595 psia = 760 Torr = 101.3250 kPa
1 Btu (I.T.) = 252.1644 calth

Units: reported values are based upon the following units with
their equivalent corresponding SI units:
mass: Pound (avdp), lbm = 0.45359237 kg
length: foot, ft = 0.3048 m
temperature: degree Fahrenheit
t/F) = 32 = [1.8(t/C)].
The Celsius scale is defined by the International Temperature
of 1990 (ITS-90), where 0C = 273.15 K.
Other derived units are:
volume: cubic foot, ft3 = 0.02831685 m3
gallon = 231 in3 = 0.0037854512 m3
pressure: pound per square inch absolute
psia = 6894.757 kPa

23-8

FIG. 23-2 (Contd)

References for the Table of Physical Constants
1. Ambrose, D., National Physical Laboratory, Teddington, Middlesex, England: Feb. 1980, NPL Report Chem 107.

24. Glasgow, A. R.; Murphy, E. T.; Willingham, C. B.; Rossini, F. D.,

J. Res. NBS, 37, 141 (1946).

2. Ambrose, D.; Hall, D. J.; Lee, D. A.; Lewis, G. B.; Mash, C. J.,
J. Chem. Thermo., 11, 1089 (1979).

25. Goodwin, R. D., Hydrogen Sulfide Provisional Thermochemical Properties from 188 to 700 K at Pressures to 75 MPa,
NBSIR 83-1694, October 1983.

3. Angus, S.; Armstrong, B.; de Reuck, K. M., Eds. Carbon Dioxide. International Thermodynamic Tables of the Fluid State-3,
Pergamon Press: Oxford, 1976.

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.

4. Angus, S.; Armstrong, B.; de Reuck, K. M., Eds. Methane. International Thermodynamic Tables of the Fluid State-5, Pergamon Press: Oxford, 1978.

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.

5. Angus, S.; Armstrong, B.; de Reuck, K. M., Propylene

(Propene). International Thermodynamic Tables of the Fluid
State-7, Pergamon Press: Oxford, 1980.

28. Goodwin, R. D.; Haynes, W. M., Thermophysical Properties of

Propane from 85 to 700 K at Pressures to 70 MPa, NBS Monograph 170, April 1982.

6. Angus, S.; de Reuck, K. M.; Armstrong, B., Eds. Nitrogen. International Thermodynamic Tables of the Fluid State-6, Pergamon Press: Oxford, 1979.

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.

7. Angus, S.; de Reuck, K. M.; McCarthy, R. D., Eds. Helium.

International Thermodynamic Tables of the Fluid State-4,
Pergamon Press: Oxford, 1977.

30. Guthrie, G. B.; Huffman, H. M., J. Am. Chem. Soc., 65, 1139
(1943).

8. Armstrong, G. T.; Jobe, T. L., Heating Values of Natural Gas

and its Components, NBSIR 82-2401, May 1982.

31. Haar, L.; Gallagher, J. S.; Kell, G. S., NBS/NRC Steam Tables,
Hemisphere Publishing Corporation, Washington, 1984.

9. Aston, J. G.; Szasz, G. J.; Finke, H. L., J. Am. Chem. Soc., 65,
1135 (1943).

32. Huffman, H. M.; Park, G. S.; Thomas, S. B., J. Am. Chem. Soc.,
52, 3241 (1930).

10. Barber, C. R., Metrologia 5, 35 (1969).

33. Hust, J. G.; Stewart, R. B., Thermodynamic Property Values

for Gaseous and Liquid Carbon Monoxide from 70 to 300 Atmospheres, NBS Technical Note 202, Nov. 1963.

11. Boundy, R. H.; Boyer, R. F., (Eds.), Styrene, Its Polymers, Copolymers and Derivatives, A.C.S. monograph No. 115, Reinholt, N.Y., 1952.

34. Jones, F. E., J. Res. NBS, 83, 419 (1978).

12. Chaiyavech, P.; Van Winkle, M., J. Chem. Eng. Data, 4, 53

(1959).

35. Keenan, J. H.; Chao, J.; Kaye, J. Gas Tables: (SI Units), John
Wiley and Sons, Inc.: New York, 1983.

13. Chao, J.; Hall, K. R.; Yao, J., Thermochimica Acta, 64, 285
(1983).

36. The Matheson Unabridged Gas Data Book, Matheson Gas

Products; New York, 1974.

14. CODATA Task Group on Key Values for Thermodynamics, CODATA Special Report No. 7, 1978.

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.

15. Commission on Atomic Weights and Isotopic Abundances, Pure

and Appl. Chem. 63, 975 (1991).

38. Messerly, J. F.; Guthrie, G. B.; Todd, S. S.; Finke, H. L., J. Chem.
Eng. Data, 12, 338 (1967).

16. Dean, J. W., A Tabulation of the Properties of Normal Hydrogen from Low Temperature to 300 K and from 1 to 100 Atmospheres, NBS Tech. Note 120, November 1961.

39. Messerly, J. F.; Todd, S. S.; Guthrie, G. B., J. Chem. Eng. Data,
15, 227 (1970).

17. Douslin, D. R.; Huffman, H. M., J. Am. Chem. Soc., 68, 1704
(1946).

40. Ohe, S., Computer Aided Data Book of Vapor Pressure, Data
Book Publishing Co., Tokyo, Japan, 1976.

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.

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).

19. Engineering Sciences Data Unit, EDSU, Engineering Sciences Data, EDSU International Ltd., London.

43. Stull, D. R.; Westrum, E. F.; Sinke, G. C., The Chemical Thermodynamics of Organic Compounds, John Wiley & Sons, Inc.,
New York, 1969.

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).

44. TRC Thermodynamic Tables ( Hydrocarbons, Thermodynamics Research Center, Texas A&M University System: College
Station, Texas.

23. Girard, G., Recommended Reference Materials of the Realization of Physicochemical Properties, Chapter 2, Marsh, K. N.
Ed.; Blackwell Sci. Pub.: London, 1987.

45. TRC Thermodynamic Tables ( Non-Hydrocarbons, Thermodynamics Research Center, Texas A&M University System:
College Station, Texas.

23-9

The table in Fig. 23-2 is followed by procedures for estimating 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 themodynamics properties for light hydrocarbons and natural gas constituents are widely available. They are routinely used by
many involved in the design and operation of natural gas processing 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 detailed 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 predicted 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 conductivities, 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 program(s). A good, reliable equation of state properly programmed and applied will always be the most convenient
method for obtaining engineering accuracy gas phase properties. Unfortunately, widespread availability and/or ease of use
are not suitable criteria for choice of an equation of state program. 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 pressure, the use of the ideal gas relationship may lead to errors
as great as 500%, as compared to errors of 2 or 3% at atmospheric pressure.
The many PVT equations of state that have been proposed
(see Section 25) for representing the pressure-volume-temperature 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 sufficiently 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 correct 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 pressuretemperature-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
=
Eq 23-2
10.73 T Z
The value 10.73 for R is used when pressure is in psia, volume in cubic feet, quantity of gas in pound moles, and temperature in R. Values of R for other combinations of units are
given in Section 1.
According to the theorem of corresponding states, the deviation 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
Critical
Pressure,
Pci, psia

Component
Molecular
Weight,
MW

Mixture
Molecular
Weight,
yi MW

Component

Mole
Fraction,
yi

Component
Critical
Temperature,
Tci, R

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

Pseudocritical
Temperature,
Tpc, R

Tpc = 392.62

Pseudocritical
Pressure,
Ppc, psia

Ppc = 661.57
G = 20.426/28.9625 = 0.705

23-10

0.543
MWm = 20.426

Reduced Temperature, Tr = T/Tc

Eq 23-3

Gas Mixtures

Reduced Pressure, Pr = P/Pc

Eq 23-4

Additional information regarding the calculation of compressibility 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.

For gas mixtures, the reduced conditions are determined using pseudocritical values instead of the true criticals:
Reduced Temperature, Tr = T/(yiTc i) = T/Tpc

Eq 23-3a

Reduced Pressure, Pr = P/(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 = (yi MWi). Calculation 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 application to the low molecular mass hydrocarbons, including methane, 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 compounds 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 50F 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 nonhydrocarbon 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. Tabulations 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 200F and 100 psia.
Solution Steps
On the P-H diagram at the intersection of the T = 200F,
P = 100 psia lines read v = 1.5 ft3/lb. Then:
= 1/1.5 = 0.667 lb.f t3
Using the EZ*THERMO90 version of the SRK91 equation of
state, is calculated to be 0.662 lb/ft3, from which
v = (1/0.662) = 1.51 ft3/lb.
For propane at 200F and 100 psia using data from Fig.
24-26
Z =

(44.10) (100)
MW P
=
= 0.936
(10.73) (458.67 + 200) (0.667)
RT

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 mixture 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 dioxide. Fig. 23-4 is applicable for temperatures 20F 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 containing appreciable amounts of heptanes and heavier components. 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 relative 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), temperatures (100 to 1000F) 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 factor 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, , 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 according to the equations:
Tc = Tc

The SRK calculation gives = 0.662 lb/ft3, and Z = 0.941.

23-11

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, , F

Pc =

Pc Tc
Tc + B (1 B)

Eq 23-6

The pseudocritical temperature adjustment factor is plotted

in Fig. 23-8. To use the factor, the pseudocritical temperature
and pressure are calculated following the procedure outlined
earlier. In this calculation, the H2S and CO2 are included as
well as hydrocarbon and other nonhydrocarbon constituents.
The pseudocritical temperature adjustment factor is read
from Fig. 23-8, and used to adjust the values of critical temperature and pressure. The reduced temperature and reduced
pressure are calculated using the adjusted values. The compressibility factor is then read from Fig. 23-4.

The pseudocritical temperature adjustment factor is read

from Fig. 23-8 to be 29.8F. The adjusted pseudocritical temperature is:
Tc = 433.9 29.8 = 404.1 R
The adjusted pseudocritical pressure is:
Pc =

(826.9) (404.1)
= 761.7 psia
433.9 + 0.2 (1 0.2) 29.8

The pseudocritical temperature and pseudoreduced

pressure are:

Example 23-2 A sour natural gas has the composition

shown below. Determine the compressibility factor for the gas
at 100F and 1000 psia.

Tr =

100 + 459.67
404.1

Z = 0.831

Solution Steps
The first step is to calculate the pseudocritical temperature
and pseudocritical pressure for the sour gas.

Comp.

Mole
Fraction

Tc, R

CO2
H2S
N2
CH4
C2H6

0.10
0.20
0.05
0.60
0.05

547.6
672.1
227.2
343.0
549.6

Pseudocritical
Tc, R
54.8
134.4
11.4
205.8
27.5
433.9

Pc, psia
1071
1300
493.1
666.4
706.5

Pr =

1000
761.7

= 1.313

(Fig. 23-4)
90

(The EZ*THERMO version of the SRK gives Z = 0.838.)

Pseudocritical
Pc, psia
107.1
260.0
24.7
399.8
35.3
826.9

= 1.385

HYDROCARBON FLUID DENSITIES

Data and Correlations
Fig. 23-9 presents saturated fluid densities (liquid and vapor) for hydrocarbons and liquid densities for some mixtures.
Fig. 23-10 is a plot of relative density as a function of temperature 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

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.

Subcooled liquid hydrocarbon densities from 50F to

+140F are shown on Fig. 23-11. Corrections to liquid hydrocarbon 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 1000F and pressures from atmospheric to 1500 psia. The petroleum fraction
is identified within the center grid by two of three characteristics API gravity at 60F, the Watson characterization
factor, Kw, or the mean-average boiling point. The mean-average 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.

At temperatures below 20F, 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)

The specific gravity of paraffinic hydrocarbons at their boiling 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 paraffinic mixtures and pure components are located according to
molecular weight.

Vol (N2 + C2 plus) =

Weight C3 plus (or H2S plus) c o mpo nents

Vo l C3 plus (o r H2S plus) components

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 60F 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. Mixtures at temperatures greater than 150F 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 densities 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 present.
Example 23-3 Fig. 23-16 illustrates the procedure outlined
above.
Density of C3 plus =

Wt (N2 + C2)
100
Wt (N2 + C2 plus)

Wt of C3 plus
44.836 lb
=
Vo l o f C3 plus
1.0128 ft3

= 44.275 lb/ft3
Eq 23-7

3. Determine the weight percent of (N2 + C2) in the (N2 + C2

plus) fraction.
Wt % (N2 + C2) =

Eq 23-10

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
(60F and 14.7 psia) on the right side of the chart.

Densityof C3 plus (or H2S plus)

=

Wt methane
100
total Wt

Wt % methane =

Density of Saturated and Subcooled Liquid Mixtures A versatile, manual procedure for calculating the

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) components, assuming additive volumes.

Wt (N2 + C2 plus)
Density (N2 + C2 plus)

6. Calculate the weight percent methane

Reduced temperatures above 0.9.

Molecular weights less than 30 (low temperature region)
and where methane is a significant part of the liquid.

The original correlation did not have a procedure for handling significant amounts of nonhydrocarbons and had a fairly
narrow temperature range of 60F to 240F. The following procedures 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 100F to 600F. Significant amounts of
nonhydrocarbons can be handled by this procedure (up to
20% N2, 80% CO2, and 30% H2S).

Eq 23-9

where

Fig. 23-13 generally predicts specific gravities within 3% of

measured values for paraffinic mixtures. However, the accuracy is somewhat less for mixtures having:

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 propane 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 60F and 14.7 psia is corrected for pressure
using a hydrocarbon liquid compressibility chart, then for temperature using a thermal expansion chart (Fig. 23-17) for hydrocarbon liquids. Experience with crude oils and rich
absorber oils shows this correlation will predict densities
within 1 to 4% of experimental data.

Wt CO2 + Wt (N2 + C2 plus)

Vol CO2 + Vol (N2 + C2 plus)

Eq 23-8

0.567

Wt % C2 in C2 plus =
100 = 1.25%
0.567
+
44.836

Density of C2 plus from Fig. 23-14 = 44.0 lb/ft3

Density of CO2 plus =

23-22

45.403 + 17.485
= 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 120F and 1760 psia
(1)
Component
Methane
Carbon Dioxide
Ethane
Propane
n-Butane
n-Pentane
n-Hexane
n-Heptane
n-Octane
n-Decane
n-Tetradecane
Total

(2)
Mole
Fraction
0.20896
0.39730
0.01886
0.02387
0.03586
0.02447
0.01844
0.02983
0.02995
0.18208
0.03038
1.00000

(3)
Molecular
Weight
16.043
44.010
30.070
44.097
58.123
72.150
86.177
100.204
114.231
142.285
198.394

(4)=(2)(3)
Weight, lb
3.352
17.485
0.567
1.053
2.084
1.766
1.589
2.989
3.421
25.907
6.027
66.240

(5)
Density (60F),
lb/cu ft

51.016

31.619
36.423
39.360
41.400
42.920
44.090
45.790
47.815

Wt % CH4 in Total =
FIG. 23-16
Density Correction for Compressibility of
Hydrocarbon Liquids

(6)=(4)/(5)
Volume, cu ft

0.3427

0.0333
0.0572
0.0449
0.0384
0.0696
0.0776
0.5658
0.1260

3.352
100 = 5.1%
66.241

Pseudodensity of mixture at 60F and 14.7 psia from

Fig. 23-14 = 42.9 lb/cu ft
Pressure correction to 1760 psia from Fig. 23-15 = +0.7
Density at 60F and 1760 psia = 42.9 + 0.7 = 43.6 lb/ft3
Temperature correction to 120F from Fig. 23-17 = 1.8
Density at 120F 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 120F 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 volume 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

(MeABP) and the molecular weight for a 56.8 API petroleum
fraction with the following ASTM distillation data.
% Over
IBP
5
10
20
30
40
50
60
70
80
90
EP

Temperature, F
100
130
153
191
217
244
280
319
384
464
592
640

IBP = initial boiling point

The significance of the various average boiling points, interconversion of D-86 and D-1160 ASTM distillations, and the
calculation of true-boiling point and atmospheric flash curves
from ASTM distillation data can be found in Chapters 3 and
4 of the API Technical Data Book.36
Molecular weight can be calculated from Eq 23-13 using MeABP in R and S (specific gravity at 60F) .

MW = 204.38 [(T)0.118] (S1.88) e(0.00218 T 3.075 S)) Eq 23-13

This relationship has been evaluated in the molecular
weight range of 70 to 720; the MeABP range of 97 to 1040F;
and the API range of 14 to 93. The average error was about
7%. Eq. 23-13 is best used for molecular weights above 115,
since it tends to over-predict below this value.
Example 23-5 Calculation of molecular weight.
From Example 23-4:
S = 0.7515 fo r 56.8 API
MeABP = 271 + 460 = 731R

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 = 325F

Refer to Fig. 23-18. Read down from a slope of 5.49 to the
interpolated curve for 325F in the set drawn with dashed
lines (MeABP). Read a correlation value of 54 on the ordinate.
Then:
MeABP = 325 54 = 271F

[e(0.00218

731) (3.075 0.7515)

= 127.0

Critical Properties
Critical properties are of interest because they are commonly used to find reduced conditions of temperature and
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

correlations for mixtures.
The following equations taken from the API Technical Data
Book36a, b can be used to estimate pseudo critical temperature
and pressure for petroleum fractions (pseudo, or undefined
components):
Ppc =

[ 3.12281 (109) T 2.3125] S 2.3201

Tpc = 24.2787 T

0.58848

0.3596

Use Eq 23-15 to calculate the pseudocritical temperature as:

Tpc = 24.2787 (271 + 460)0.58848 (0.7515)0.3596
= 1062R or 602F
Fo r this 56.8API fluid,estimate the pseudo c ritic al pressure, using Eq 23-14 and MeABP = 271F:

Eq 23-14

Ppc =

Eq 23-15

These equations are in terms of T = MeABP (R) and specific

gravity (S) at 60F. Both of these correlations have been evaluated over the range of 80 to 690 molecular weight; 70 to 295F
normal boiling point; and 6.6 to 95 API.
Example 23-6 Pseudocritical temperature and pressure.
Take the previous mixture (from Example 23-4) with:
VABP = 325F
MeABP = 271F
API = 56.8
Molecular Weight = 127 (Ex. 23-5)
ASTM D-86, 10% to 90% Slope = 5.49
Find its pseudocritical temperature.
Solution Steps
From Fig. 23-18 with ASTM D-86 slope = 5.49 find a VABP
correction of about 85F (extrapolated from the left-hand
group).
MABP = 325 85 = 240F

[ 3.12281 (109)] (271 + 460)2.3125 (0.7515)2.3021

= 386 psia

Acentric Factor
The acentric factor, , is frequently used as a third parameter in corresponding states correlations. It is tabulated for
pure hydrocarbons in Fig. 23-2. Note that the acentric factor
is a function of Pvp, Pc, and Tc.
It is arbitrarily defined by
= log (Pvp/Pc) Tr = 0.7 1.0

Eq 23-16

This definition requires knowledge of the critical (pseudocritical) temperature, vapor pressure, and critical (pseudocritical) pressure.
For a hydrocarbon mixture of known composition, and containing similar components, the acentric factor may be estimated, with reasonable accuracy, as the molar average of the
individual pure component acentric factors:
= xi i

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

23-30

Eq 23-17

FIG. 23-23
Hydrocarbon Gas Viscosity

23-31

Ppc = 356 psia

If the vapor pressure is not known, can be estimated38 for

pure hydrocarbons or fractions with boiling point ranges of
50F or less, using Eq. 23-18.
3 log Pc log 14.7
=
1.0
Tc

7
T 1

From Eq. 23-15, the pseudocritical temperature is:

Tpc = 24.2787 (875)0.58848 (0.871)0.3596

Eq 23-18

Tpc = 1244R
3 lo g (356) log (14.7)
=
1.0 = 0.447
1244

7
875 1.0

Example 23-7 Acentric factor.

A narrow-boiling petroleum fraction has a VABP of 418F,
an ASTM slope of 0.75 and an API gravity of 41. Estimate its
acentric factor.
In order to use Eq 23-18 we need the average boiling point
(MeABP); the pseudocritical temperature (a function of
MABP); and the pseudocritical pressure (a function of MeABP).
From Fig. 23-18, the correction to VABP for mean average
is 3F; the correction for MABP is 5F. Note that for narrowboiling fractions, all boiling points approach the volumetric
average. Then, MeABP = 415F and MABP is 413F.

Vapor Pressure
The vapor pressures of light hydrocarbons and some common inorganics in the temperature range below 100F are
given in Fig. 23-19. Vapor pressures at higher temperatures,
up to 600F, are given in Fig. 23-20 for the same compounds.
Note that, except for ethylene and propylene, the hydrocarbons are all normal paraffins.

VISCOSITY

From Eq. 23-14, the pseudocritical pressure is:

T = 415 + 460 = 875R
S for 41API = 141.5/(131.5 + 41) = 0.871
Ppc =

[ 3.12281 109 (875)2.3125] (0.871)2.3201

Figs. 23-21 through 23-29 give the viscosity of hydrocarbon

liquids and vapors, water, steam, and miscellaneous gases. Fig.
23-21 gives data on hydrocarbon liquids. Figs. 23-22, 23-23 and
23-24 present data on hydrocarbon gases. To correct for pressure,
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 preferred when the reduced temperature is greater than 1.0. Fig.
23-28 gives the viscosity of hydrocarbon liquids containing dissolved gases. Note that Fig. 1-7 gives conversion factors for
viscosity.

Calculation of Gas Mixture Viscosity

Example 23-8Determine the viscosity of a gas of molecular
weight 22 at 1,000 psia and 100F. Tc = 409R, Pc = 665 psia
Solution Steps
id

Hence, the viscosity at 1000 psia and 100F is:

= (1.21) (0.0105) = 0.0127 centipoise
The viscosity of a gaseous mixture with large amounts of
nonhydrocarbons is best determined by using the method
of Dean and Stiel.41 This method is particularly useful for
handling natural gas with high CO2 content. Tested against
30 CO2-N2 mixtures, it had an average deviation of 1.21%
at pressures up to 3525 psia. It makes use of a factor, ,
defined as:
1/6

(Tcm)
= 5.4402
2/3

MW
P
(

(x
)
(
)
)

i
i
cm

= 22/28.964 = 0.760

From Fig. 23-23 at 100F:

A = 0.0105 centipoise
100 + 460
= 1.37
409

Eq 23-19

If the reduced temperature Tr is > 1.5, then

A = [166.8 (105)] [(166.8 105)(0.1338 Tr 0.0932)5/9]

Then:
Tr =

Pr =

1000
= 1.50
665

Eq 23-20

Note: Pseudocritical temperature and pressure should be

calculated as outlined in this section, if the composition of the
gas is available.

If Tr is 1.5,

Because Tr > 1.0, Fig. 23-24 is preferred to obtain the correction for elevated pressure to the viscosity at one atmosphere.

In either case, A is found by dividing ( A) by .

Equations 23-19 through 23-21 will predict the viscosity of pure
gases as well as mixtures. To apply the Dean and Stiel41 method
to mixtures, the pseudocritical volumes, compressibilities, and
temperatures are calculated by the Prausnitz and Gunn42 mixing
rules:

From Fig. 23-24:

= 1.21
A

A = 34.0 105 (Tr 8/9 )

23-33

Eq 23-21

Vcm = (yi Vc i)

Eq 23-22

B = 1105.7

Zcm = (yi Zci)

Eq 23-23

Tcm = (yi Tci)

Eq 23-24

11.99
= 0.02645
A = 101.78 (325 + 459.67) 0.175 29.263
1105.3

The same constants are employed at 100F and at 210F.

Zcm R Tcm

Pcm =

Eq 23-25

Vcm

1.8 (1105.7)

= 0.02645 e

Example 23-9 For a temperature of 50F and a pressure of

300 psia, estimate the viscosity of a mixture of 80 mole percent
methane, 15 mole percent nitrogen, and 5 mole percent carbon
dioxide. Calculations are summarized in Fig. 23-30:

(0.2875) (10.73) (335.9)

= 663.4 psia
1.562
Substituting from the calculation table in Fig. 23-30 into
Eq 23-19:
(5.4402) (335.9)1/6

(19.237)1/2 (663.4)2/3

Tr =

1.8 (1105.7)
669.67

= 0.926 cs at 100F
= 0.517 cs at 210F

The reported values are 0.93 and 0.52 centistokes, respectively.

Zcm R Tcm
=
Vcm

Pcm

= 0.02645 e

559.67

= 0.043

T
509.7
=
= 1.517
Tcm
335.9

Because Tr > 1.5, the expression to be used for A is Eq 2320.

THERMAL CONDUCTIVITY
Thermal conductivity for natural gas mixtures at elevated
pressure can be calculated from an atmospheric value and a
pressure correction. Figs. 23-31 through 23-36 present low
pressure thermal conductivity data of gases developed from
published data.51, 54 The pressure correction of Lenoir et al.52
shown in Fig. 23-32 is applied to these low pressure data as
illustrated below. The thermal conductivity of liquid paraffin
hydrocarbons is plotted in Fig. 23-35 and the thermal conductivity of liquid petroleum fractions in Fig. 23-36.

A = 166.8 (105) [0.1338 Tr 0.0932]5/9

FIG. 23-27

= 166.8 (105) [(0.1338) (1.517) 0.0932]5/9

Water Viscosity at Saturated Conditions

A = 48.91 (105)
A = 0.01138 centipoise
Using Fig. 23-23 and correcting for the nitrogen and carbon
dioxide content of this mixture gives a A 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% volume distilled.
= A e1.8 B / T
A = (101.78 Tb 0.175 29.263)

Eq 23-26
Kw
B

ln (B) = 4.717 + 0.00292 Tb

Eq 23-27
Eq 23-28

Example 23-10 At 100F and 210F find the viscosity of a

heavy condensate having a mid-boiling point of 325F and a
specific gravity of 0.7688.
Solution Steps
3

Kw

325 + 459.67

=
= 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 100F and One Atmosphere

23-35

k/kA = 1.15

FIG. 23-29
Viscosity of Steam

46, 47

k = (1.15) (0.0248) = 0.0285 Btu/[(hr sq ft F)/ft]

Another method for estimating thermal conductivity is presented by Stiel and Thodos.53
To determine the thermal conductivity of a gaseous mixture
of defined components, the thermal conductivity of each component at the given temperature is read from the charts provided 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 containing CO2 because the thermal conductivity goes through a
maximum.

MW
i)
(yi ki
3

km =

Eq 23-29

MW
yi

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 determined 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 200F and one atmosphere.
km =

0.05774
= 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 preceding 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 experimental data.
Example 23-11 Find the thermal conductivity of a 25 molecular weight natural gas at 700 psia and 300F. Tc = 440R,
Pc = 660 psia

SURFACE TENSION
The interior molecules of a liquid exert upon the surface
molecules an inward force of attraction which tends to minimize the surface area of the liquid. The work required to enlarge the surface area by one square centimeter is called the
surface free energy. The perpendicular force in the liquid surface, called surface tension, exerts a force parallel to the plane
of the surface. Surface tension, an important property where
wetting, foaming, emulsification, and droplet formation are
encountered, is used in the design of fractionators, absorbers,
two-phase pipelines, and in reservoir calculations.

Solution Steps
From Fig. 23-31, at 300F:
kA = 0.0248 Btu/[(hr sq ft F)/ft]
Tr = (300 + 460)/440 = 1.73
Pr = 700/660 = 1.06
From Fig. 23-32:

FIG. 23-30
Calculation of Viscosity of a Gas Mixture
Mole
Fraction
CH4
N2
CO2
Mixture

0.80
0.15
0.05
1.00

Molecular
Weight

Tc, R

Pc, psia

VC,
cu ft/lb mole

16.043
28.013
44.010

343.0
227.2
547.6

666.4
493.1
1071.

1.59
1.43
1.51
1.562

23-36

Zc =

PcVc
10.73 Tc

0.2879
0.2892
0.2752
0.2875

Vcm = yiVci
1.272
0.215
0.076
1.562

Tcm = yiTci MWm = yiMWi

274.4
34.1
27.4
335.9

12.834
4.202
2.201
19.237

FIG. 23-31

FIG. 23-32

Thermal Conductivity of Natural and Hydrocarbon Gases

at One Atmosphere (14.696 psia)

Thermal Conductivity Ratio for Gases

Pure Components

Values for Hv and MWi are obtained from Fig. 23-2.

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:

m =

1 2
1 x2 + 2 x1

Eq 23-30

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 compressibility 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 standard temperature and pressure in which all water formed appears 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 = (yiHvi)

Eq 23-31

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 produced 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 temperature and pressure of the gas) to the density of dry air (at
the air temperature and pressure).
MW P Ta Za

Eq 23-32
=
G =
MWa Pa Z
s
The ideal gas specific gravity is the ratio of the molecular
weight of the gas to the molecular weight of dry air.
MW
Eq 23-33
Gid =
MWa
For a mixture
G id = (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 composition is not available.

23-37

FIG. 23-33

FIG. 23-34

Thermal Conductivity of Miscellaneous Gases

at One Atmosphere59, 60, 61, 62

Thermal Conductivity of Hydrocarbon Gases

at One Atmosphere67, 68, 69

G id =

G (Pa T Z)
MW
=
P Ta Z
MWa

Eq 23-35

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 is

water saturated but the component analysis is on a dry basis,
the component analysis must be adjusted to reflect the presence of water. The mole fraction of water in the mixture is
estimated as:
yw =

nw
Pow
=
(on a one mole basis)
p
(1 + nw)

The adjusted mole fractions are calculated using the following equation:
Pow

yw
= yi (1 yw)
i = yi 1
P

Eq 23-36

When the gas is wet but not water saturated and the component analysis is on a dry basis, it is necessary to determine
the water content and to adjust the mole fractions to reflect
the presence of water. When the water mole fraction, yw, is
known, the adjusted mole fractions can be obtained from
Eq 23-37.
The yiw values are used in the gross heating value and gas
compressibility calculations after adding water to the component list. If the dry gross heating value is known, the effect of
the water content can be calculated using:
Eq 23-38
Hv (wet) = (1 yw) Hv (dry) + 50.3 yw

Calculations Additional details on these calculational

methods and examples are given in GPA Standard 2172, Calculation of Gross Heating Value, Relative Density and Compressibility Factor for Natural Gas Mixtures from
Compositional Analysis. A listing of the Basic source code for
a computer program to perform the calculations is given in
2172.

For water saturated gas, water is added to the component

list and the xw
i values are used in the gross heating value and
the gas compressibility calculations. If the dry gross heating
value is known, the water saturated gross heating value can
be calculated by:
1.7051 29.94

1.7051
Hv (satd) = 1
Hv (dry) +

P
P

Eq 23-37

23-38

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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

Component

Mole
Fraction

Thermal
Conductivity
Btu/[(hr sq ft F)/ft]

Molecular
Weight

MW
i

(yi

MW
i)

(yi ki

MW
i )

CO2

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N2

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CH4

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C2H6

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3.109

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0.00274

Total

1.00

2.8220

0.05774

FIG. 23-38
Surface Tension of Paraffin Hydrocarbons85

23-40

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23-42