Physical Properties of Petroleum Fractions: Appendix L

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APPENDIX L

Physical Properties of
Petroleum Fractions

In the early 1930s, tests were developed that characterized petroleum oils
and petroleum fractions so that various physical characteristics of petroleum
products could be related to these tests. Details of the tests can be found in
Petroleum Products and Lubricants, an annual publication of Committee D-2 of
the American Society for Testing Materials.1 These tests are not scientifically
exact, and hence the procedure used in the tests must be followed faithfully
if reliable results are to be obtained. However, the tests have been adopted
because they are quite easy to perform in an ordinary laboratory and
because the properties of petroleum fractions can be predicted from the
results. The specifications for fuels, oils, and so on are set out in terms of
these tests plus many other properties, such as the flash point, the percent
sulfur, and the viscosity.
Over the years various phases of the initial work have been extended,
and development of a new characterization scheme using the pseudocom-
pound approach is evolving. Daubert2 summarizes the traditional and new
methods insofar as predicting molecular weights, pseudocritical tempera-
ture and pressure, acentric factor, and characterization factors.
In this appendix we present the results of the work of Smith and Wat-
son and associates,3 who related petroleum properties to a factor known as
the characterization factor (sometimes called the UOP characterization factor). It
is defined as
(TB)1/ 3
K =
S

1Report of Committee D-2, ASTM, Philadelphia, annually.


2T. E. Daubert, “Property Predictions,” Hydrocarbon Proc., 108–10 (March, 1980).
3R. L. Smith and K. M. Watson, Ind. Eng. Chem., 29, 1408 (1937); K. M. Watson and

E. F. Nelson. Ind. Eng. Chem., 25, 880 (1933); K. M. Watson, E. F. Nelson, and G. B. Murphy,
Ind. Eng. Chem., 27, 1460 (1935).
893
894 Appendix L Physical Properties of Petroleum Fractions

where K = UOP characterization factor


T = cubic average boiling point, ºR
S = specific gravity at 60ºF/60ºF
Other averages for boiling points are used in evaluating K and the other physi-
cal properties elsewhere on the CD. (Refer to Daubert4 or Miquel5 for details.)
This factor has been related to many of the other simple tests and properties of
petroleum fractions such as viscosity, molecular weight, critical temperature,
and percentage of hydrogen, so that it is quite easy to estimate the factor for
any particular sample. Furthermore, tables of the UOP characterization factor
are available for a wide variety of common types of petroleum fractions, as
shown in Table L.1 for typical liquids.

Table L.1 Typical UOP Characterization Factors

Type of Stock K Type of Stock K

Pennsylvania crude 12.2–12.5 Propane 14.7


Mid-continent crude 11.8–12.0 Hexane 12.8
Gulf Coast crude 11.0–11.8 Octane 12.7
East Texas crude 11.9 Natural gasoline 12.7–12.8
California crude 10.98–11.9 Light gas oil 10.5
Benzene 9.5 Kerosene 10.5–11.5

Refer to the charts of the hydrocarbons that give (a) the specific heats,
(b) the vapor pressure, (c) the heat of combustion, (d) the API, and (e) the
heats of vaporization.

4M. R. Riazi and T. E. Daubert. Ind. Eng. Chem. Res., 26, 755–759 (1987).
5J. Miquel and F. Castells. Hydrocarbon Processing, 101–105 (Dec. 1993).
Appendix L Physical Properties of Petroleum Fractions 895

Table L.2 Information Concerning Charts in Appendix L

1. Specific heats of hydrocarbon liquids


Source: J. B. Maxwell. Data Book on Hydrocarbons (p. 93). New York: Van Nostrand Rein-
hold, 1950 (original from M. W. Kellogg Co.).
Description: A chart of Cp (0.4 to 0.8) vs. t (0 to 1000ºF) for petroleum fractions from 0 to
120º API.
Boiling-point basis: Volumetric average boiling point, which is equal to graphical
integration of the differential ASTM distillation curve (Van Winkle’s “exact method”).
Limitations: This chart is not valid at temperatures within 50ºF of the pseudocritical
temperatures.
2. Vapor pressure of hydrocarbons
Source: Maxwell, Data Book on Hydrocarbons, p. 42.
Description: Vapor pressure (0.002 to 100 atm) vs. temperature (50 to 1200ºF) for
hydrocarbons with normal boiling points of 100 to 1200ºF (C4H10 and C5H12 lines
shown).
Boiling-point basis: Normal boiling point (pure hydrocarbons).
Limitations: These charts apply well to all hydrocarbon series except the lowest-boiling
members of each series.
3. Heat of combustion of fuel oils and petroleum fractions
Source: Maxwell, Data Book on Hydrocarbons, p. 180.
Description: Heats of combustion above 60ºF (17,000 to 25,000 Btu/lb) vs. gravity (0 to
60ºAPI) with correction for sulfur and inerts included (as shown on chart).
4. Properties of petroleum fractions
Source: O. A. Hougen and K. M. Watson. Chemical Process Principles Charts (Chart 3).
New York: Wiley, 1946.
Description: ºAPI(-10 to 90ºAPI) vs. boiling point (100 to 1000ºF) with molecular weight,
critical temperature, and K factors as parameters.
Boiling-point basis: Use cubic average boiling point when using the K values; use mean
average boiling point when using the molecular weights.
5. Heat of vaporization of hydrocarbons and petroleum fractions at 1.0 atm pressure
Source: Hougen and Watson, Chemical Process Principles Chart, Chart 68.
Description: Heats of vaporization (60 to 180 Btu/lb) vs. mean average boiling point (100 to
1000ºF) with molecular weight and API gravity as parameters.
Boiling-point basis: Mean average boiling point.
896 Appendix L Physical Properties of Petroleum Fractions

Figure L.1 Specific heats of hydrocarbon liquids.

Figure L.2 Vapor pressure of hydrocarbons.


Appendix L Physical Properties of Petroleum Fractions 897

Figure L.3 Heat of combustion of fuel oils and petroleum fractions.


898 Appendix L Physical Properties of Petroleum Fractions

Figure L.4 Properties of petroleum fractions.

Figure L.5 Heats of vaporization of hydrocarbon and petroleum


fractions at 1.0 atmosphere pressure.
Appendix L Physical Properties of Petroleum Fractions 899

Properties of Petroleum Fractions


900 Appendix L Physical Properties of Petroleum Fractions
Appendix L Physical Properties of Petroleum Fractions 901

Sources of Equations

1. J.F. Fallon and K.M. Watson, “Thermal Properties of Hydrocarbons,” Nat. Pet.
News (Tech. Sec.), p. R-372 (June 7, 1944).
2. R.H. Cavett. “Physical Data for Distillation Calculations-Vapor-Liquid Equilibria,”
Proc. Am. Pet. Inst. Div. Refining, v. 42. p. 351 (1962).
3. K.M. Watson, “Thermodynamics of the Liquid State,” Ind. Eng. Chem. V. 35,
p. 398 (1943).

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