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NBS SPECIAL PUBLICATION 434

U.S. DEPARTMENT OF COMMERCE / National Bureau of Standards

ydrocarbons for Fuel75 Years of Materials

Research at NBS

C
NATIONAL BUREAU OF STANDARDS

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Applied Mathematics — Electricity — Mechanics — Heat — Optical Physics — Center

for Radiation Research: Nuclear Sciences; Applied Radiation — Laboratory Astrophysics ^ — Cryogenics — Electromagnetics ^ — Time and Frequency °. THE INSTITUTE FOR MATERIALS RESEARCH conducts materials research leading to improved methods of measurement, standards, and data on the properties of well-characterized

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1 Headquarters and Laboratories at Gaithersburg, Maryland, unless otherwise noted; mailing address Washington, D C. 20234.

2 Located at Boulder, Colorado 80302.
or BTANBABJDfil

LIBKAJST

JUN 1 4 1976

Hydrocarbons for Fuel75 Years of Materials Research at NBS

George T. Armstrong

Physical Chemistry Division

Institute for Materials Research

National Bureau of Standards

Washington, D.C. 20234

U.S. DEPARTMENT OF COMMERCE, Elliot L. Richardson, Secretary

James A. Baker, III, Under Secrefary

Dr. Betsy Ancker-Johnson, Assisfanf Secrefary for Science and Technology

5 NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Acting Director

Issued May 1976
Library of Congress Cataloging in Publication Data

Armstrong, George Thomson, 1916-

Hydrocarbons for fuel—75 years of materials research at NBS.

(National Bureau of Standards special publication ; 434)

Bibliography: p. Supt. of Docs, no.: C 13.10:434

1. Fuel research—United States. 2. Hydrocarbon research

United States. 3. United States. National Bureau of Standards

History. I. Title. H. Series: United States. National Bureau of Standards. Special publication ; 434. QC100.U57 no. 434 LTP343] 602'.ls

[662'.6] 75-619428

National Bureau of Standards Special Publication 434

Nat. Bur. Stand. (U.S.), Spec. Publ. 434, 20 (May 1976)

CODEN: XNBSAV

U.S. GOVERNMENT PRINTING OFFICE

WASHINGTON: 1976

For sale by (be Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402

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Contents

Page

1. Introduction 1

1.1. Gaseous fuels 1

1.2. Liquid petroleum and petroleum products 1

1.3. Solid fuels 2

1.4. Standard reference materials 2

2. Methane and natural gas 2

2.1. Industrial gas measurement, analysis, and calorimetry 2

2.2. Physical and thermodynamic properties of pure components and well-defined mixtures

of components 4

3. Liquid petroleum products 5

3.1. Densities and enthalpies of combustion 5

3.2. Composition of petroleum and properties of its components 7

3.3. Experimental thermochemistry of pure hydrocarbons 9

3.4. Standard reference data on pure hydrocarbons 10

3.5. Other work on petroleum fuels 12

4. Solid fuels—Thermodynamic studies on coal, coke, graphite, diamond, and substances related

to their combustion 12

5. Standard reference materials for hydrocarbon fuels 13

5.1. Hydrocarbon blends 13

5.2. Reference fuels 13

5.3. Lead in reference fuels 13

5.4. Sulfur in fuel oil 13

5.5. Heating values of hydrocarbon fuels 13

6. Coal reference materials 14

6.1. Trace mercury in coal 14

6.2. Sulfur in coal 14

6.3. Trace elements in coal 14

6.4. Trace elements on coal fly ash 14

7. Conclusion 14

8. References 15

iii

Hydrocarbons for Fuel—

75 Years of Materials Research at NBS

George T. Armstrong

In this historical review the NBS work on hydrocarbons is discussed in terms of the three major classes of natural hydrocarbonaceous fuels: natural gas, petroleum, and coal. The work

done on the measurement of properties of the pure components has included measurement of the values of the properties themselves and development of practical and accurate measurement

procedures and instruments. In addition, combustion energies, densities, viscosities, vapor pressures, refractive indices, elemental compositions and other parameters have been determined for complex fuel mixtures and correlated to find methods of estimating properties. Extensive standard

reference data tables have been compiled and a number of standard reference materials have

been developed.

Key words: Coal; energy; fuel; graphite; hydrocarbons; metering; methane; natural gas;

petroleum; physical properties; standard reference materials.

1. Introduction

The scope of NBS work on hydrocarbons for fuels over ihe years is so broad and complex that a brief

review such as this can only point out highlights. Let

us briefly outline first some of the principal features

of the NBS fuel hydrocarbons work.

More or less broad coverage has been given to all the fossil fuels. The work has covered natural gas and

petroleum more extensively than coal; however, even

here some interesting and perhaps little appreciated

work has been done. In each of these areas the practical fuels themselves have been studied, as well as well-characterized substances of which they are composed. Significant effort has gone into the measure- ment of properties of the pure components, both

from the point of view of establishing the values of

the properties themselves and from the point of view

of practical and accurate measurement devices and

procedures. In addition, combustion energies, densities, viscosities, vapor pressures, refractive indices,

elemental compositions and other parameters have

been determined for complex fuel mixtures and correlated to find methods of estimating one or more

properties. The studies date from the earliest days of

NBS, when natural gas was coming into widespread

use as a fuel and beginning to displace gas manufactured from coal. Several very intensive well defined

programs of research at NBS have revolved around

the properties of gaseous and liquid hydrocarbon

fuels. Extensive standard reference data compilations

have been prepared, and a number of standard refer- ence materials, related to the use of hydrocarbons

Jnd hydrocarbonaceous materials as fuels, have been

developed and are in use.

In this review, work on hydrocarbons at the National

Bureau of Standards is discussed in terms of the three

najor classes of natural hydrocarbon or hydrocarjonaceous fuels: natural gas, petroleum, and coal.

1.1. Gaseous Fuels

In the early days of NBS which was founded in

1901 natural gas was just coming into service as a

domestic heating and cooking fuel, its prior use having been mainly for illumination. Early NBS work

was directed to the goals of safety and quality in this

new fuel, and to measurement of its properties. Studies

included methods of measurement of gas quantities

(volumetrically ) and of density, measurement of heating value and candlepower, and determination of

impurities. Circulars were prepared describing how

these could be determined accurately. For the States the NBS also tested calorimeters for measuring the

heating value of gaseous fuels. In later years NBS

evaluated automatic calorimeters for continuous re- cording of gas heating values.

One important result of NBS work has been the

adoption of heating value as the measure of a gaseous

fuel in trade: this is the current practice. In order to provide measurement validity a reference material (a

good quality methane) is certified for real-gas heating

value provided at intervals by NBS for the Institute

of Gas Technology, which is the present source of

reference fuels for the fuel gas industry.

Currently under way at NBS (Boulder) is a study,

supported by the American Gas Association and other

institutions, to provide better experimental data on

the properties of liquefied natural gas. The properties

of the principal pure components and of their binary

and more complex mixtures are being determined.

1.2. Liquid Petroleum and Petroleum Products

For liquid petroleum and its components NBS has

carried out, with the support of the American Petroleum Institute or of the Defense Department, several

long-term studies, some of which have had major

impact on U.S. and world petroleum technology. The

studies include densities and coefficients of expansion

of naturally occurring petroleum and refinery products, and their energies of combustion, heat capacities, and enthalpies of vaporization. The studies of

density and coefficient of expansion form the initial basis of the widely used petroleum measurement

tables, which are used in gauging quantities of petroleum products in transportation, transfer and storage.

A new survey of densities and coefficients of expansion

1
of petroleum and refinery products representative of

the world-wide sources is in progress.

It was found to be possible to correlate energy of

combustion with various easily measured parameters

such as aniline point and specific gravity; and several

tables have been prepared, which are widely used in

the industry for estimating heating values of well defined grades of commercial fuels such as aviation

gasoline, jet fuels, and kerosines.

Procedures and instruments for accurate measure- ment of energies of combustion, freezing points, and

purities of pure hydrocarbons were developed. Under

the American Petroleum Institute Research Project 6,

extensive studies were made of the composition of

petroleum. More than two hundred high-purity hydrocarbons were prepared, and the purities of these materials were established. For more than a hundred

hydrocarbons, accurate determinations of boiling

points and vapor pressures, densities, refractive in- dices, freezing points, and energies of combustion were made. These form the classical studies of petroleum and hydrocarbons.

Under the American Petroleum Institute Research

Project 44 was carried on a review and critical evaluation of the properties of the pure hydrocarbons determined from all published work. These reviews provided selected values of twenty-two different thermodynamic and physical properties for some twenty-five

classes of hydrocarbons. The studies included correlation of properties in homologous series, and the

calculation of thermal functions and equilibrium constants of the gases from statistical thermodynamic

principles. An example of the use of the equilibrium

constants of formation that were calculated is the

prediction of equilibrium proportions of isomeric hydrocarbons.

In the NBS Thermochemical Laboratories, definitive studies were also made of the energies of formation of the principal products of combustion of all hydrocarbon fuels: H-O, CO, and COo.

1.3. Solid Fuels

With respect to coal components, the principal re- lated work at NBS has been definitive studies of the

energies of combustion of synthetic and naturally oc- curing graphite and diamond and of the relationship

of these to the energy of combustion of coke containing various amounts of hydrogen. Studies have also

been made of the thermal properties of graphite to elevated temperatures.

1.4. Standard Reference Materials

Standard reference materials for use in natural gas

technology, petroleum fuel technology, and coal combustion technology have been developed and are

available. Some of these relate to the properties of

the fuels themselves; others refer to pollution problems created by their use. Examples of the latter are standard samples for analysis of trace heavy metals in

coal and coal ash. and sulfur in fuel oil and coal.

2. Methane and Natural Gas

2.1. Industrial Gas Measurement, Analysis,

and Calorimetry

Study of natural gas began at NBS as part of an

extensive program guided by E. B. Rosa (1901-1921)

in the early years of NBS to establish standards of

safety, quality, measurement, and performance, in the

public utilities industries. Natural gas was in transition from its principal use for illumination to its later use for heating [1].^ At the turn of the century gas was measured to individual customers by volume and

charged for on that basis. Important properties were "candlepower" and "heating value." E. B. Rosa almost

immediately began advocating the use of heating

value as a measure of quality and value of natural gas

[2]. Heating value was ultimately adopted as the measure of the commodity as a result of this NBS

activity [1]. The procedure is still in practice.

Early NBS work included studies of the measure- ment of quantity of gas (M. H. Stillman [3]; see also

[4]) ; measurement of heating value (C. W. Waidner

and E. F. Mueller [5] ) ; determination of candlepower

[6] ; determination of impurities, in particular am- monia [7] and hydrogen sulfide [8] ; determination

of gas density [9]. Other aspects of commercial gas

technology were also involved, including safety and

fittings for gas service.

Calorimetry of gaseous methane on a routine basis

required the conduct of the combustion process in a reproducible way, the use of commercial gas calorimeters (such as the Junkers or the Boys calorimeters ) - together with commercial gas metering de- vices (usually the wet test meter), and associated

temperature and mass measurements. The process was

fairly complex for a routine quality-test procedure.

It consisted of measuring volumetrically the amount

of gas flowing into the system, burning the gas with

a controlled amount of combustion air in the calorimeter, in which the heat was absorbed in flowing

water, and observing the heat affect of the combustion

when a steady state was achieved.

The NBS studies established the conditions for

carrying out the measurements accurately, with in- accuracies lying between 0.2 and 0.5 percent. Factors

requiring measurement or control include temperature, pressure, and humidity of the gas, amount of gas

burned, amount of combustion air used, degree of

completeness of combustion, rate of water flow in the

calorimeter, temperature rise of the flowing water in the calorimeter, heat losses due to extraneous processes, and mass of water condensed from the combustion gases. With heating value proposed as a criterion of value

for trade in natural gas, methods for determining it and adequate auxiliary data for interpreting the

measurements were needed. These were prepared as

^ Figures in brackets refer to literature references at the end of this publication.

- Certain trade names and company products are identified in order to adequately specify the experimental procedure. In no case does such identification imply recommendation or endorsement by the National Bureau of Standards, nor does it imply that the products arc necessarily the best available for the purpose.

2
NBS Circulars: Standard Methods of Gas Testing

(Circular No. 48 [4]) and Gas Calorimeter Tables

(Circular No. 65, revised and reissued at intervals as Circulars C417 and C464) [10].

The NBS also undertook to test calorimeters for

the States that adopted heating value as a measure

for pricing fuel. This was to provide regulatory commissions with the necessary equipment and measure- ment verification to enable them to test fuels and ap- prove of charges by public utilities corporations.

Although the gas-flow calorimeter is an absolute in- strument for which calibration is not appropriate,

demonstration of the accuracy of the complete process in a particular calorimeter required analysis of

combustion gas and products and a careful mathematical treatment of the results. This was a relatively

time consuming process. The testing of manually operated calorimeters for the States continued until

about 1955, when the number tested annually had

become very small. The gas industry by that time had

almost universally adopted the automatic recording

calorimeter and this accounted for the absence of

manually operated instruments.

The automatic recording gas calorimeter of the type

principally in use in the United States was the subject

of two extensive investigations at NBS. R. S. .Jessup

[11] compared the Thomas Recording Calorimeter

(later called Cutler-Hammer Automatic Recording

Calorimeter) with the Junkers calorimeter, and established the reliability of the former as being well within

1.0 percent. Figure 1 shows the Cutler-Hammer calorimeter schematically. The calorimeter suffered to a certain extent from a lag in responding to sudden

changes of heating value of the gas. However, the

convenience of use and the continuous record obtained

provided sufficient incentive to cause this calorimeter

and its later versions to displace the manually operated calorimeters.

J. H. Eiseman and E. A. Potter [12] later established that with gas of high heating value (methanelike) the calorimeter could provide measurements

with uncertainties of 0.25 percent or less. Their study

was necessitated by the higher heating value of gases

that had come into the market since the earlier study.

The Cutler-Hammer calorimeter operates on the

following principle. Gas is burned at a constant rate and the heat developed is absorbed by a stream of air. The rates of flow of the gas, the air for combustion,

and the air for absorption of heat are regulated by

metering devices similar to the ordinary wet-gas

meter. These metering devices are geared together and

driven by an electric motor so that the ratios of the

three rates of flow are constant. The products of combustion are kept separate from the heat-absorbing air

and are cooled very nearly to the initial temperature

of the air. The water formed in the combustion is condensed to the liquid state. The rise in temperature

of the heat-absorbing air is proportional to the total or gross heating value of the gas. The rise in temperature is measured by means of resistance thermometers

and is recorded graphically.

Gas calorimeters of the above type, with public

reliance justified by these NBS studies, give the basis

for calculating heating values of fuels delivered to the

homeowner and exchanged in trade between producers, transmission companies, and industrial or

public utilities consumers. The above problems have been primarily metrology problems and relate primarily to the adequate

measurement of important parameters of this com- monly used fuel. Other work at NBS has provided

further important information for the fuel gas trade. In the period of World War I (see ref. [61]) the

NBS became involved intensively in measures for

conservation and rationing of natural gas. Toward the end of the war period the necessity of

obtaining helium from natural gas created a need for

measurement of physical and thermodynamic properties of methane as a cryogenic fluid, in order to establish conditions for separation of methane from

the helium. This led to an initiation of studies on the

physical properties of methane [16] such as the vapor

pressure measurements by Cragoe [62, 63b] which

are comparatively obscure.

ON RANGES 0-700 BTU AND BELOW

PIPING SHOWN DOTTED .S NOT USEO^^^^ THERMOMETER

•B' PRIMARY i GAS 8 PRIMARY C"ECK TUBE , AIR I AIR. MIXTURE v /

DRAIN MANIFOLDS DRAIN POT

DRAIN POT WATER LEVEL F

Figure 1. Flow diagram of the Cutler-Hammer recording gas calorimeter.

3
2.2. Physical and Thermodynamic Properties

of Pure Components and Well-Defined

Mixtures of Components

With the discovery of deuterium in 1932 by Urey,

Brickwedde, and Murphy [34], the theoretical interest in isotope effects led Brickwedde and Scott to undertake a study of the thermodynamic properties

of deuterated methanes. This work, including the

original vapor pressure work on CH4 by Cragoe, un- published for many years, was finally summarized by

Armstrong and published [63]. The vapor pressure

study of the deuteromethanes is unique in the number

of closely related deuterium-substituted molecules for

which precise data were reported, and showed a strong

and very regular isotope substituent effect. Three of the most important thermochemical studies

made by F. D. Rossini, and among his earliest studies at NBS, were the definitive determinations of the

enthalpies of combustion of hydrogen [13], methane

[14], and carbon monoxide [14]. Not only are these

substances important ingredients of commercial fuels,

but the products of combustion, water and carbon

dioxide, are universal products of combustion of hydrocarbon fuels. The enthalpies of formation of the

products are essential in fuel energy calculations.

Rossini's studies reduced the uncertainties in the

combustion energies by a factor of three or more. These studies were followed by other studies covering

the principal hydrocarbon constituents of gaseous

fuels, the low-molecular-weight aliphatic hydrocarbons

ethane, propane, and the butanes. The measured values

are generally accepted as standard reference data for

the ideal gas hydrocarbons. See later for additional

calorimetric measurements by Rossini and his col- leagues. In further support of the combustion calorimetry of

natural gas as a pricing measurement, a standard

reference material consisting of a natural gas of good

quality was certified as to its heating value and issued

by NBS for some years. This reference material is used in the industry to verify the accuracy of calorimeters in the natural gas range of heating values. The

responsibility for distribution of this reference material was transferred to the Institute of Gas Technology

in 1961, with the provision that NBS would supply a certification of a reference fuel as needed to provide

traceability of the energy measurement to the national

standards.

The last certification of such a reference material was prepared in 1965 [15]. The material certified was analyzed by mass spectrometric and gas chromatographic techniques by E. E. Hughes and J. K. Taylor.

It was about 99.95 percent methane, with 0.04 percent

ethane and much smaller amounts of non-combustible

constituents. The heating value was calculated for

unit volume of the real gas both dry and water-satu- rated under the standard pressure and temperature

conditions in use by the gas industry. The calculation,

which was done by G. T. Armstrong, was based upon

Rossini's determination of the standard enthalpies of

combustion of methane and ethane (adopted as stan- dard reference data), the compressibility data of Douslin (Bureau of Mines) and the vapor pressure of water

measured by H. F. Stimson (NBS).

Calculation of the heating value of gas mixtures

from composition has long been considered attractive as an alternative to calorimetry for many purposes

requiring less than the highest accuracy. To meet the

needs of the gas industry in particular, and to prepare users for coming metric practice, a recommended

set of values of combustion energies of the ideal

gases was prepared in 1972 [16]. This compilation

gives heating values on a dry and on a water-satu- rated basis for ideal gases: H2, H2S, CO, CH4, and

49 other selected gaseous hydrocarbons (Ci to Co) in

kilojoules per mole, megajoules per cubic meter, and

British thermal units per cubic foot. Values are tabulated under two standard conditions: 288.71 K

(60 °F), 101591.3 N • m"-^ (30 in Hg) used for many

years by ASTM; and 288.71 K (60 °F), 101559.8

N • m~^ (14.73 psia) recently proposed by ANSI. An

outline is given of a procedure to derive data for the

real gases, and to adjust temperature and pressure

bases. In deriving these values, advantage was taken of a recent critical review and compilation by E. S. Domalski [65.] of the enthalpies of combustion of organic

substances including many hydrocarbons. This re- view was a partial updating of the well knov/n compilation made at NBS by Kharasch [66], which for

many years stood as the only extensive authoritative

collection of enthalpies of combustion of organic

compounds.

Within recent years, research on natural gas and

liquefied natural gas has been resumed at the NBS

Boulder laboratories to meet the needs resulting from

large scale use liquefied natural gas (LNG). This

extensive progrp.n has several tasks which are still underway.

One of the most significant contributions of this

program has been new, comprehensive, accurate data on thermophysical properties of compressed and liquefied methane, the predominant constituent of natural

gas. A recent publication by R. D. Goodwin [17] covers the temperature region from 90 to 500 K at pressures to 70 MPa. It gives a critical evaluation and

correlation of all relevant equation-of-state and ther- modynamic data, original equation-of-state and heat

capacity measurements, and comprehensive accurate

tables of thermodynamic data.

Other work completed in this program includes new

measurements and correlations of data on heat capacities [18], sound velocities [19], dielectric constants

[20], refractive indices [21], viscosities and thermal

conductivity coefficients [22. 23] of methane in the

temperature range 90 to 300 K, and pressures to 35

MPa.

With respect to mixtures of compressed and liquefied constituents of natural gas, the most significant

contribution to date from this group is a comprehensive bibliography of experimental data by M. J. Hiza,

et al. [24]. Also, new liquid-vapor equilibrium mea- surements have been reported for methane-nitrogen

mixtures in the temperature range 95-180 K [25, 26].

4
Other projected work includes measurements of

densities of liquid methane, ethane, propane, butane,

nitrogen and mixtures of these substances, and methods for estimating heating values of flowing LNG.

3. Liquid Petroleum Products

3.1. Densities and Enthalpies of Combustion

Among the properties of petroleum that are most

important conmiercially are the density and coefficient

of expansion. They are widely used in the measure- ment of shipments of petroleum. Ten million cubic

meters (approximately sixty million barrels) of crude

petroleum are measured each day as it enters the

world market, and similar quantities of petroleum

products are delivered in various stages of processing.

The measurement of much of this material is made

volumetrically. To assure that the measured amounts

of material are equitable for trade, despite fluctuations

in density due to thermal expansion, the measurements

are adjusted to a reference temperature. (60 °F or 15 5/9 °C has been used for many years. A change

to 15 °C is currently under way.) The adjustments are made using internationally accepted petroleum measurement tables [27], which are based on average

measured coefficients of expansion of petroleum and

petroleum products. These measurement tables have

been largely based on NBS measurements in the past

and indications are that they will continue to be so

based.

NBS involvement in the petroleum measurement

tables began with experimental density determinations

in the period 1912 to 1914 by H. W. Bearce and E. L. Peffer [28]. They made determinations on refined

oils, crude oils, fuel oils and heavy lubricating oils,

representing the commercial petroleum oils produced

in the United States at that time. Densities were determined by hydrostatic weighing and by picnometer

at 0, 10, 20, 25, 30, 40, 50, 75, 85, and 95 °C. The

data for each fuel were fitted to equations of the form = Z)r + a{t — T) + p(i — 7)2

which were found to represent the data closely. In

these equations J" is a reference temperature such as 25 °C and i is a variable temperature. The coefficients a and (3 thus found vary regularly on the average

with the density at 25 °C (D-^--,) . For their historical

interest, the plotted data from this research are shown

as figure 2. In retrospect, the qualitative statistical treatment of the data in this paper appears to be hardly

adequate in view of the fact that the deviations from

the selected curve are large compared to the total range of the curve and the fact that the smoothed

values were to be used to measure materials from all the sources involved, and others.

Smoothed densities from the above paper were

transformed to specific gravities (determined in air)

and degrees Baume and tabulated in various ways to allow volumes measured at ambient temperature to be reduced to volumes and weights at the reference

Figure 2. Summary data of Bearce and feffer showing the variation of coefficients of expansion

with density ( at the reference temperature) for petroleum oils.

5
temperature. Thus treated they formed the first authoritative United States Standard Tables for Petroleum Oils [29]. The justification for using smoothed

tables for measuring oils showing such wide individual deviations is that on the average the measurement

errors will cancel, a justification whose validity has

been questioned from time to time.

Additional experimental measurements of thermal

expansion of petroleum oils were made by R. S. Jessup

[30] and of gasolines by C. S. Cragoe and E. E. Hill

[31]. These studies were undertaken to provide data on materials prepared using cracking processes not

encountered in the earlier study. Jessup's study indicated that the viscosity of an oil and its density provided good correlating parameters for estimating vol- ume as a function of temperature and pressure. The

work of Cragoe and Hill showed systematic differences

in the thermal expansions of cracked gasolines and

straight run gasolines. Distillation curves provided a

better correlating device than the specific gravity.

The work that went into the preparation of the

Standard Petroleum Oil Tables (NBS Circular 57 and

its successors C154, C410, and finally the ASTM-IP

Petroleum Measurement Tables) is described by

Hyams and Holmes [32].

Diversification of world petroleum resources in re- cent years has led to renewed speculation as to the

validity of the averages. A new, extremely comprehensive survey of densities and coefficients of thermal

expansion of crude and refined petroleum representing known supplies has been inuagurated and is under

way at the National Bureau of Standards (1975).

The new survey links densities to the prototype SI

units. The measurements on oil samples are based

upon the natural oscillation frequency of a tube filled with the liquid under investigation [33]. This technique is sensitive enough to detect changes of less than

a part per million in density.

Other thermal properties of petroluem also vary

systematically with temperature, with the density, and

with other parameters associated with the oils. A

substantial amount of work was carried out at NBS

to establish equations and tables of data that would

represent averages for petroleum products.

An early and very well known and widely used

example of this is NBS Miscellaneous Publication No.

97, "Thermal Properties of Petroleum Products." This

publication prepared by Cragoe [34] gives tables and

discussion of thermal expansion, energies of combustion, specific volume of vapor, thermal conductivity, specific heat capacity, enthalpy of vaporization,

and enthalpy of a range of petroleum oils. This publication was prepared primarily as a critical review and

summary of data in the literature, compiled at the

initiation of American Petroleum Institute (API)

Project 38, which began in 1927 at NBS (see note

following reference [34] ) . This compilation proved

to be very popular and calls for it are still received

forty years later. It is still one of the few, if not the

only, source of federally authorized average data for

hydrocarbon fuels in certain regions of density. In the above publication energies of combustion

were tabulated as functions of the gravity (degrees

API ) . The API gravity is a Baume scale of reciprocal

specific gravity, modulus 141.5.^ The use of API

gravity is widespread in the petroleimi industry; and

NBS staff found it convenient to assist this technology

in the succeeding years, by establishing other correlations based on it. Several studies were carried out for

the U.S. Air Force to provide correlations for esti- mating the enthalpy of combustion of aviation fuels

of various grades. The work carried out over a period

of years ending in 1962 apparently was initiated by

C. S. Cragoe as part of API project 38. However, it was continued primarily by R. S. Jessup and included

studies of aviation gasoline (several grades), jet fuels,

and kerosine. The latter work [35] provided the basic

data for the kerosine fuel used in first stage engines

of such rockets as Atlas and many others. These

studies were adopted by the American Society for

Testing and Materials, by the Institute of Petroleum,

the American National Standards Institute, and the

Federal Government as standard methods of test for

estimating the net heat of combustion of specified

fuels, based on the so-called aniline-gravity product

(product of aniline point temperature in degrees Fahrenheit and specific gravity in degrees API). See

Annual Book of ASTM Standards [36] for the cor- relations adopted and their sources. From a scientific point of view the above studies

leave much to be desired. The correlating parameters

could be only very qualitatively related to the quantity

of interest—the enthalpy of combustion to gaseous

water, carbon dioxide, sulfur dioxide, and nitrogen.

The aniline point (the minimum solution temperature

of an equivolume mixture of aniline ajid the liquid

under test) is a rough measure of aromatic hydrocarbon content in mixed hydrocarbon fuels, and to a

lesser extent a measure of naphthenic hydrocarbons.

These have significantly lower specific enthalpies of

combustion than have aliphatic hydrocarbons and dif- ferences from each other because of variations in hydrogen content, hydrocarbon chain length, ring size,

and degree of ring formation, all of which affect the

enthalpy of combustion. The parameters correlated do

not show as good a correlation for pure hydrocarbons

as they do for the naturally occurring and derived

mixtures. Thus the success of the correlation schemes

depends on the presence of large numbers of hydrocarbons to provide reasonably constant and regularly

varying average values. Within well defined classes of

fuels the correlations allow estimation of the enthalpy

of combustion within 55 kj/kg (23 Btu/lb) at the 95

percent confidence level (approximately 0.15 percent

uncertainty in the enthalpy of combustion).

Better and more rationally justified correlations

have been obtained, based on analysis for hydrocarbon type and assignment of a characteristic enthalpy

of combustion to each hydrocarbon type [35]. For

practical purposes this improvement helps not at all; the necessary measurements are as complex as the

combustion measurement itself.

''The functional relationship is: Gravity/degrees API = 141.5/ (sp gr 60/60 F) —131.5. where sp gr 60/60 F is the specific gravity at 60''F with respect to water at 60'F.

6
A technical problem arises in attempting to make

these correlations useful in nations using SI measurements. The conversions are not trivial in terms of the

amount of effort involved compared to the length of

the test itself. Recorrelations based on SI measure- ments would probably be more satisfactory.

The current interest in energy thrift together with

the high prices of fuels revived interest in reliable

information about enthalpies of combustion of burner

fuels and diesel fuels. However, the chances of success

in empirical correlations of the types given above are diminished because of the high molecular weights of

the substances of which they are composed. The more

complex molecules of which these materials are composed permit a wider range of energies of combustion

because of more possibilities for polycyclic aromatics

and naphthenes. The paraffinic and asphaltic base

petroleums also differ more as the residuals are in- cluded. Heavy oils derived from shale or coal are

different from those derived from petroleum. Their

composition and properties may vary greatly with

conditions of their formation (temperature, hydrogen

pressure, etc.)

.

3.2. Composition of Petroleum and Properties

of its Components

American Petroleum Institute Research Project 6 was carried out at the National Bureau of Standards,

and in its course made a notable contribution to the

fractionation, analysis, isolation, purification, and

properties of petroleum hydrocarbons. This project was initiated in January 1927, with E. W. Washburn,

Chief of the Division of Chemistry as its first Director,

followed in 1934 by F. D. Rossini, who continued as

its Director after it was transferred from NBS to the

Carnegie Institute of Technology in June 1950. A detailed summary account of the work of this project was given by Rossini, Mair, and Streiff [37]. The

remarkable scope of this work is hinted at from a

listing of chapter headings which is given in table 1. The principal investigators on this work, under Washburn, 1927-34, were Mair, White, Leslie, Schicktanz,

Rose, Bruun, and Hicks-Bruun, and, under Rossini,

from 1934, were Mair, Forziati, Willingham, Glasgow,

Streiff, Krouskop, and Camin.

The monograph and the technical papers of this

work are noteworthy for their meticulous analysis of

procedures and mathematical formulations, the in- tricacy and the detailed description of instruments,

apparatus, and experimental results. As examples are shown in figure 3a and 3b the boiler used to determine boiling points, and the manometer assembly

used to regulate the boiling point pressure at 20 fixed

points. In the course of their work, the project scientists

made accurate measurements of boiling points and

vapor pressures on 119 different compounds in the

range 5 to 105 kPa (40 to 785 mm Hg), with the

pictured apparatus. These data were fitted with Antoine (3 constant) equations. Standard deviations of

temperature were 0.001 to 0.002 K, and of the pres- sure 2.5 to 5 Pa (0.02 to 0.04 mm Hg).

Table 1. Chapter headings of Hydrocarbons from

Petroleum [37].

1. Introduction

2. Fractionation and Fractionating Processes

3. Regular Distillation

4. Azeotropic Distillation

5. Regular Distillation at Different Pressures

6. Distillation at Very Low Pressures

7. Extraction

8. Adsorption

9. Crystallization

10. Solid Molecular Compounds, Clathrate Compounds

11. Boiling Points and Vapor Pressures

12. Densities

13. Refractive Indices

14. Freezing Points; Evaluation of Purity from Freezing

Points

15. Molecular Weights

16. Analysis for Carbon and Hydrogen

17. Purification of Hydrocarbons

18. Summary of the Work of Other Laboratories on the Composition of Petroleum

19. Analysis of the Gasoline Fraction of Petroleum

20. Analysis of the Kerosine Fraction of Petroleum

21. Analysis of the Gas-Oil Fraction of Petroleum

22. Analysis of the Lubricant Fraction of Petroleum

23. Hydrocarbons in One Crude Petroleum

24. Hydrocarbons in Different Crude Petroleums

25. Analysis of the Hydrocarbons in Certain Gasoline Distil- lates

26. Analysis of Alkylates and Hydrocodimers

27. Analysis of Codimers

Appendices and Indices

Densities were measured at 20, 25, and 30 °C for

115 hydrocarbons, with overall uncertainties estimated

at about 50 \ig ' cm""*^. In the freezing point studies a method was developed for estimating impurities, of sufficient simplicity

that it could be used in the routine test laboratory. In addition to the compounds for which freezing points

are listed in table 2, the study found fifteen com- pounds that could not be crystallized.

As part of the above program, a cooperative sample

preparation program involving twenty-seven laboratories was carried out. As a result of this program,

over two hundred different hydrocarbon substances were prepared as standard hydrocarbons or research

hydrocarbons having measured purities. The participating laboratories included the NBS group, Ohio

State University, Pennsylvania State College, NACA

Flight Propulsion Laboratory, General Motors Corporation, California Research Corporation, Phillips Petroleum Company, Standard Oil Development Company, Atlantic Refining Company, and Ethyl Corporation, supplying from 3 to 99 samples each, and

sixteen other laboratories supplying one or two

samples each. The collection of materials, the preparation and purification of additional materials, and

the management of their distribution was transferred

to the Carnegie Institute of Technology in 1950.

The hydrocarbons were prepared at NBS under the

direction of Rossini, with B. J. Mair as the principal

supervisor, principally by regular distillation and

azeotropic distillation, with occasional use of distilla- ation at reduced pressure, adsorption, crystallization,

and fractionation with urea. Purity changes during

7
purification were followed by measurements of freezing points. In the course of the work, reliable procedures were developed for preserving the samples by

sealing under vacuum in glass ampoules.

Of the more than two hundred different compounds

that thus became available as research materials, well over half were obtained in purities greater than 99.9

mole percent. Essentially all had purities greater than

99.5 percent. These became the basis of extensive

physical properties measurements of high quality. In

table 2 are summarized the principal archival measurements of physical properties as distinguished from

the large numbers of test data measured for process

control in the preparation of the materials.

Figure 3a. Details of the boiler and related parts of the

boiling-point apparatus.

The letters have the following significance: A, tube through which the sample

is introduced; B, platinum resistance thermometer; C, stopcock; D, con- densers; E, ground glass valve for withdrawing distillate; F, thermocouple,

for measuring difference in temperature between the wall of the glass boiler and the jacket; G, metal control for the ground-glass valve; H, receiver for recovering sample at the conclusion of the measurements; I, receiver for collecting distillate removed from the head during the experiment; J, glass well for the platinum resistance thermometer; K, radiation shield of alu- minum foil; L, electric heater for boiling the liquid in the pot; M, jacket 1/4 in wall, of aluminum; N, tube for withdrawing sample from the pot; 0, thermal insulating jacket, Pyrex glass cylinder with an asbestos layer covered

with aluminum foil; P, flat electric heater for the aluminum jacket; Q.

transite support; R, thermal insulation, covered with aluminum foil; W, glass rod supports for the thermometer v/ell; X, glass rod "spiders"; Y, connecting

tube for equalizing pressure; Z, transite collar for centering boiler.

The other aspect of the program of API Project 6 was the fractionation, analysis, and isolation of hydrocarbons from petroleum. Before this project began,

only a few low boiling hydrocarbons such as propane,

n-butane, isobutane, n-pentane, and isopentane had

been isolated from petroleum and identified. In the

early days of the project the distilling columns used

for gasoline fractionation had a separating power

equivalent to about 20 theoretical plates. By the time

the project transferred away from NBS distilling

H zL

Figure 3b. Manometer assembly, showing the air thermostat.

The letters have the fallowing significance : A, box enclosure with walls of transite (the cover is not shown ) ; B, aluminum foil, covering inside and

outside surface of the transite box; C, partial partition wall of transite (both

sides covered with aluminum foil: serving to guide flow of air; D, rotary air circulator ; E, electric motor, mounted independently of the tliermostat housing; F, electric space heater, 100 watts; G, mercury manometer; H, con- nection to electric power through relay contacts; I, connection to relay coil;

J, mercury thermoregulator ; K, connection to pressure system; L, mercury8
Table 2. Physical properties measurements on pure hydrocarbons under API Project 6.

r roperty

Number of hydrocarbonsRange of values

•

• Uncertainties Utner

Boiling point ° 20 points Antoine

vapor pressure 119 c t 1 rtC 1 T>_ 5 to 105 kra 2.5 to r> ra equations

Density " 115 20, 25, 30 "C 50 /ig'cm"'

Refractive 20, 25, 30 "C Hartman equation

Index 119 7 v^ravelengths 0.0001 Couchy equation

Freezing -160 to +80 °C Cryoscopic constant. point normal aim air iiLipuriiy pressure

Principal investigators in addition to Rossini, Mair, and StreifE [37]. C) Willingham, Taylor, Pignocco, Forziati, Norris, and Camin, see [37, pp. 188-208]

C) Forziati and Camin, see [37, pp. 209-219]

(') Forziati and Camin, see [27, pp. 220-238]

(") Glasgow and Krouskop, see [37, pp. 239-281]

columns with about 200 theoretical plates were used

by the project. (These numbers of plates, of course,

are hardly comparable to the much more effective

separating capability of a gas-liquid chromatograph

of the 1970's.)

The separation procedures adopted in Project 6 for

the gasoline fraction of petroleum included (1) an initial adsorption stage by which the aromatic hydrocarbons were separated from the parrafin and naphthene

hydrocarbons and (2) a distillation process to resolve

each of these two components separately. The distilla- tion of the_ two pQrtions yielded directly (a) concentrates of pure compounds, or (b) concentrates of mixtures of two or more compounds. The constant boiling

mixtures of compounds of the same type were resolved

by further distillation (regular or azeotropic) or by

crystallization. The constant boiling mixtures of paraffin and naphthene hydrocarbons were separated by

special procedures. Non-hydrocarbon components,

such as sulfur compounds, were concentrated with the

aromatic fraction and were separated by further adsorption. The key feature in simplifying the separation

process was the initial segregation of aromatic and

non-aromatic portions, which greatly mitigated the

difficulties of the later fractional distillations. Separation procedures were also devised for the kerosine

fraction, gas-oil fraction, and the lubricant fraction

of petroleum.

Using the above procedures devised and tested on

the Project, a single representative crude petroleum was analyzed in detail in one of the most complex

and sustained chemical analyses in history. The sample was 600 gallons (2.5 m^) of a Midcontinent crude

petroleum from Ponca City, Oklahoma (courtesy of

the Maryland Oil Company, later part of Continental

Oil Company) selected to be intermediate in composition in terms of then known petroleums from differ- ent fields. The sample was taken in 1928 and bv 1952

one hundred thirtv compounds had been isolated, most

of them identified and their relative abundances determined.

The number of compounds actually found in significant amounts is a small fraction of those for which

physical properties would place them in the ranges

analyzed. As an example, of perhaps 500 petroleum

compounds in the boiling range 40 to 180 °C, 92 were

isolated. These constitute 82 percent of the gasoline

fraction; so the remaining >400 compounds must

have been present in relatively small amounts.

The analysis of this single petroleum was unique

at the time it was being done. We shall not here

attempt to place this in perspective in terms of current

(1975) knowledge of the composition of petroleum.

While we have not seen extensive analyses of these

types reported, we would presume that the highly

sophisticated analytical techniques now available and

in the hands of private institutions have led to ex- tensive additions to information about the composition

of petroleum from various fields.

3.3. Experimental Thermochemistry of Pure

Hydrocarbons

The availability of so many highly purified hydrocarbons as a result of API Project 6, combined with

highly developed calorimetric techniques and instruments already available, presented a unique opportunity to carry out definitive experimental determinations of the energies of combustion of the compounds

and to derive enthalpies of formation. An extensive

series of investigations was carried out by Rossini

and later by Prosen and colleagues, working with

Rossini : over one hundred different hydrocarbons

were studied in the period 1931-1955. In approximately the same period Jessup, working independently,

measured several hydrocarbons from other sources. The hydrocarbons ranged from CH4 to Cir,H-)4 (nhexadecane) . Measurements on n-heptane by Prosen

and Rossini [38] may be taken as a typical example.

As a result of twenty experiments A//c(25 °C) was

found to be 4817.14 kj • mof-i (4816.35 int kj • mol~^) with standard deviation of the mean of 0.004

percent and an estimated uncertainty (95 percent confidence limits) of 0.018 percent. Typical uncertainties

in enthalpies of formation were ^1 kJ • mol^^.

9
The necessary techniques for carrying out the ac- curate experimental calorimetric studies were developed at NBS. Dickinson in a classical paper [39]

described an accurate bomb calorimeter and how it had been tested for possible sources of error. This

calorimeter design, with minor modifications over the

years, was used for all of the studies described above.

The Dickinson calorimeter is pictured in cross section

in figure 4. One of the calorimeters identified by

inventory number in [39] is in the possession of the

NBS Museum. The calorimeter was used in the very

earliest work for certification of standard substances

for calibrating bomb calorimeters. The calorimeter

itself consisted simply of a stirred water container in

which a reaction vessel was immersed; the assembly was surrounded by and isolated from a constant

temperature (±0.001 K) jacket.

in accounts scattered through many papers in the

literature. Rossini [40b], Coops, Jessup, and Van Nes

[40a] and Prosen [40c] summarized the procedures.

The elaborate procedure for reducing data for the

reaction as observed in the calorimeter to the value

for the isothermal process with the substances in their

standard thermodynamic states was developed at NBS

by E. W. Washburn [41] and is known in practice as "the Washburn Correction."

For some of the combustion work on commercial

fuels at NBS (see above), which was done in the same calorimeters, but with somewhat less attention to refinements of the measurements, Jessup [42] pre- pared a detailed guide to procedures. This is perhaps

the most concise guide available for measurements on commercial fuels, and formed the basis of an ASTM

Standard [43] suitable for measurements with inaccuracies of 0.1 percent or less.

Figure 4. Dickinson Calorimeter Cross Section.

Parts of the calorimeter are lettered as follows: A, therniostated air-box (optional); B, stirred water jacket; C, inner wall of jacket; D, outer wall

of calorimeter vessel; E, platinum-resistance thermometer; F, air space; G,

calorimeter bomb; H, electrical calibration heater; I, arrows showing direc- tion of water circulation; J, stirring well of calorimeter vessel; K, jacket temperature sensor; L, calorimeter-vessel stirrer; M, jacket stirrer; N, jacket

heater.

The measurements were precision measurements

requiring the best thermometry available, uniform

operating conditions, and extreme care in sample

preparation, weighing, characterization of sample,

establishment of reaction vessel contents, estimation of

amounts and states of reaction products, and reduction of the data. Both constant volume (bomb) and

constant pressure (flow) reactions were determined,

depending upon the volatility of the combustion

sample. The procedures were described in some detail

3.4. Standard Reference Data on Pure

Hydrocarbons

Another very important project carried out at NBS

was API Project 44. This project was initiated in

1942 to compile tables of selected values of properties

of hydrocarbons. The program involved collaboration

of scientists at NBS and the University of California.

The principal scientists involved were F. D. Rossini,

Director, K. S. Pitzer, W. J. Taylor, J. P. Ebert, M.

G. Williams, H. G. Werner, C. W. Beckett (Berkeley,

CA), J. E. Kilpatrick, B. Epstein, L. Arnett, R. Braun.

Regular NBS staff who consulted on the project were

C. S. Cragoe, E. J. Prosen, and D. D. Wagman. The

results of the investigations appeared periodically as technical articles (many in NBS Journal of Research),

as looseleaf tables of data and spectrograms and as bound volumes. All tables prepared as of 1947 ap- peared in an NBS Monograph [44]. This project con- tinued at NBS until June, 1950, when it was transferred

to the Carnegie Institute of Technology, to remain

under Rossini's guidance until 1960. The work continues at present (1975) under the leadership of B. J. Zwolinski in the Thermodynamic Research Center at Texas A and M University.

The above group of investigators made a very careful compilation of selected values of physical and

thermochemical properties of hydrocarbons. For this

work, all pertinent original data in the literature, and

all available unpublished data were appraised criti- cally; values of given properties were correlated with

temperature, pressure, and molecular structure; original calculations of thermodynamic and physical properties were made as necessary; "best" values of the

properties were selected and tabulated in convenient

form; and some of the procedures and calculations were published. The properties reviewed are listed in

table 3. As of 1947, a total of 347 pages of tables had

been prepared. In addition to compilations of the

above data, infrared and ultraviolet spectrograms for

hydrocarbons and related compounds were collected.

The classes of compounds for which data were

tabulated in reference [44] are listed in table 4.

10
Table 3. Physical properties of hydrocarbons evaluated and

tabulated in API Project 44 [44].

1. boiling point and pressure coefi&cient of the boiling point

2. refractive index

3. density and specific gravity

4. freezing point

5. molar volume

6. molar refraction and specific refraction

7. specific dispersion

8. refractivity intercept

9. viscosity

10. critical constants

11. P-V-T relations

12. vapor pressures

13. enthalpy and entropy of vaporization

14. enthalpy of combustion

15. enthalpy

16. Gibbs energy function

17. molar heat capacity

18. enthalpy of formation

19. equilibrium constant of formation

20. enthalpy and entropy of fusion

21. cryoscopic constants

22. enthalpy of transition

Table 4. Classes of hydrocarbons and related compounds for which thermodynamic and physical properties data were

tabulated in API Project 44 [44].

00 0, H, N, C

0 O2, H2, OH, H.O, N2, NO, C, CO, CO2

1 Paraffins, Ci to Cs (8 substances)

2 Paraffins, Co to C7 (14 substances)

3 Paraffins, Cs (18 substances) 4 Paraffins, Cg (35 substances)

5 Alkylbenzenes, Ce to Co (14 substances)

6 Alkylcyclopentanes, Cs to C7 (8 substances)

7 Alkylcyclohexanes, Co to Cs (10 substances)

8 Monoolefins, C2 to Co (29 substances)

9 Monoolefins, C7 (36 substances)

10 Monoolefins, Cs (92 substances)

11 Diolefins, C3 to Co (32 substances)

12 Acetylenes, C2 to Cs (7 substances)

13 Styrenes, Cs to Co (4 substances)

14 Alkylbenzenes, Cio (22 substances)

15 Alkylcyclopentanes, Cs (15 substances)

16 Alkylcyclohexanes, Co

17 Paraffins, Cio 18 Alkylcyclopentenes, Cs to C7

19 Alkylcyclohexenes, Ce to Cs

20 Normal paraffins, Ci to CTM (20 substances)

21 Normal alkylbenzenes, Co to C22 (17 substances)

22 Normal alkylcyclopentanes, C-, to Cci (27 substances) 23 Normal alkylcyclohexanes, Co to Q2 (17 substances)

24 Normal monoolefins (1-alkenes), C2 to C20 (19 substances)

25 Normal acetylenes (1-alkynes), C2 to C20 (19 substances)

The published calculations and correlations in- cluded: Gibbs energies and equilibria of isomerization of isomeric hydrocarbons [45], enthalpies, equilibrium constants, and Gibbs energies of formation of

selected hydrocarbons as functions of temperature to 1000 or 1500 K [46] ; normal coordinate analyses

[47] of hydrocarbon molecules. (References are to selected examples.)

The presence of the resulting large amounts of

numerical data on homologous series of compounds

and compounds showing well defined compositional

and structural variations, such as the isomeric forms,

the presence of multiple bonds, and cyclization, has

encouraged many individual attempts in NBS and

elsewhere to devise correlations. Generally these cor- relations have as their primary goal s.ufficient understanding of the effects of these structural and compositional variations to permit estimation of the properties of other substances not measured. Done properly

and carefully, such correlations can frequently yield

values more reliable than many investigators can measure them. They are sometimes used to screen measured data in a search for errors. The correlations

also assist in establishing theoretical models relating

the structure and properties of materials.

An example of a correlation derived from measured

values is found in Prosen and Rossini [48], [48a].

See also Taylor, Pignocco, and Rossini [48bl. The

values for the enthalpies of combustion of the liquid

normal paraffins above pentane for reference [44] were obtained by fitting an equation linear in the

number of carbon atoms, n, to the experimental data

which were available for thirteen substances of which

hexadecane has the largest molecule. The resulting

equation

-A//c (298.15 K) /kcal-mol-i = -57.909 +

157.443 n with an uncertainty of (0.1647 - 0.03902 n + 0.00268 n2)^, n>5

i -A^c(298.15 K)/kJ-mol-^ = -242.291 +

658.741 n with an uncertainty of (2.883 - 0.6831 n -f

0.0469 „>5 ^ was used to calculate the unmeasured values for nor- mal paraffins through n-eicosane. Analogous correlations of other properties were also used in completing

the tables of reference [44].

The reason for putting estimated data in the tables

is to provide the working technologist with a value

selected by an experienced observer rather than leave

him to cope alone with unknown values. The scientist

interested in testing a new correlation scheme should

be wary to seek out only measured data and not base

his test on smoothed or other estimated data, as some

have done unwittingly.

The configurational analysis of the substituted cyclohexanes by Pitzer and Beckett [49] showed that at ordinary temperatures substantially all the molecules

are in the chair configuration of the cyclohexane nucleus, and described in detail the resulting tautomeric

forms. One interesting result of this analysis was that

among the 1,3-dimethylcyclohexanes, the isomer having the lower energy content must be the "cis" isomer

and the isomer having the higher energy content must

be the "trans" isomer. This designation [50] reversed

the previous labeling of these isomers.

Another interesting illustration of the results of the

statistical thermodynamic calculations made on the

hydrocarbons is seen in figure 5. This shows the mole

fractions of the six methylstyrenes at chemical equilibrium as functions of temperature. There is a significant decrease in alpha-methylstyrene and compensating

increases in beta-methylstyrene and ortho-methylsty- rene as the temperature rises above 300 K.

11
TEMPERATURE IN °C 0 200 400 600 800 1000 1200

400 600 800 OOO 1200 MOO

TEMPERATURE IN °K

Figure 5. Equilibrium concentrations of the six methylstyrenes.

The scale of ordinates measures the relative amount (mole fraction) and the

scale of abscissas gives the temperature in kelvins, and degrees Celsius. The vertical width of a band at a given temperature measures the mole

fraction of the given isomer present at equilibrium with all of its oiher isomers in the gaseous state.

3.5. Other Work on Petroleum Fuels

In addition to the work on petroleum and petroleum

components as materials, there was a long substantial

program on engine fuels, which was primarily carried

out by F. L. Howard and his colleagues in the Automotive Section (Heat and Power Division). The work

of this section was complex and dealt with much more

than the fuels themselves, including also the interactions of the fuels with the automobile engine.

Topics with which they dealt included: knock rat- ings of gasolines, cetane ratings of diesel fuels: fouling

of spark plugs; kinetics and mechanisms of the combustion process in flames and in detonations of hydrocarbons; synthesis and characterization of special

hydrocarbons; analysis and testing of hydrocarbon

mixtures.

A major and somewhat analogous study of the lubricant fractions of petroleum were studied by 0. C. Bridgeman, S. A. McKee and their associates in the

Heat and Power Division. Rheology of petroleum and

viscosity standards were intensively studied.

Other work which may be mentioned was done during World War I. Studies were made of aviation gasoline and substitute or mixed fuels [61a], and of the

recovery of toluene from natural gas [61c].

4. Solid Fuels — Thermodynamic Studies

on Coal, Coke, Graphite, Diamond, and

Substances Related to Their Combustion

Coal as a mineral hydrocarbonaceous fuel and its component compounds have received comparatively

little attention at NBS as compared to gaseous and

liquid fuels. In addition to the reference materials for coal discussed later, however, one subject closely related to coal will be mentioned here. This is the studies of the

thermodynamic properties of graphite and diamond.

Coal as a hydrocarbonaceous material is, of course,

clearly distinguishable from graphite. Nevertheless,

coal itself has structural features similar to graphite;

and when coal is carbonized by coking or other charring processes these similarities are enhanced.

For this reason the thermodynamic properties of

graphite are important particularly for the future uses

of coal, in which its chemical transformation to gas- eous and liquid fuels on a large scale is contemplated.

The thermochemical equilibria involved may have to refer to differences of coal from graphite as a rea- sonable baseline, because of the variable character of

coal and its chars.

For another reason, graphite is important not only

for coal but for liquid and gaseous hydrocarbon fuels as well. The process of combustion of all of these fuels

leads to carbon dioxide as a principal product, and

the energies of formation and molecular binding en- ergies of all the hydrocarbons depend upon the combustion energy of graphite which is the reference state of the element carbon.

The experimental studies on elemental carbon at NBS include: (1) the heat capacity of graphite from

about 1200 K to about 2600 K [51a] (West and

Ishihara) and 1500 K to 3000 K [51b] (Cezairliyan) ; (2) the energy of combustion of diamond [52] (Jessup) ; (3) the energy of combustion of graphite [52]

(Jessup, also Prosen and Rossini).

The experimental studies on the energy of combustion of graphite were carried out in an informal

joint experimental program with the Coal Research

Laboratory of the Carnegie Institute of Technology.

In this program the NBS work was complemented by

a careful study of the combustion energies of anthracite cokes and of artificial and natural graphites, by

Dewey and Harper [53] of the Coal Research Laboratory. Jessup also measured the combustion energy

of diamond at this time.

Prior to this research, because of the variability of

the data on graphite, the thermodynamic reference

state for carbon had been taken as diamond (Bichowski and Rossini) [59]. However, the work of Dewey

and Harper and of Jessup showed that, by a simple

purification, either natural or artificial graphite can be produced in a thermodynamically reproducible

12
form. Because of its greater accessibility, ease of handling, and lower cost, graphite was then chosen as the

reference state for carbon. As a result of the work

mentioned above and of the measurements on graphite

a few years later by Prosen and Rossini, the enthalpy

of formation of CO. (g) from graphite has been taken

to be 393.513 kj-mol-i (-94.0518 kcal/mol) [54].

See for instance Wagman, et al. [55, 56] and Sunner

[57].

Using data largely obtained from NBS experimental

work, Wagman, et al. [55] calculated enthalpies, Gibbs

energies and equilibrium constants of some of the

most important reactions in fuel combustion: those

involving Oo, Ho, H,0, C, CO, COo, and CH4. Eight

reactions were treated in the reference cited.

Of considerable interest still today is the extensive

work on anthracite coke by Dewey and Harper.

Among other information they derived was the variation of energy of combustion with hydrogen content. The variations in hydrogen content were created by

different coke formation temperatures ranging from

900 to 1300 °C. The absorptive capacities for carbon

dioxide were also determined. An essentially linear

relationship is observed between heating value and

hydrogen content, but no credible relationship was

found between heating value and absorptive capacity.

One final mention can be made of the NBS work on

graphite. For some years a study was made of the

energetic effects of radiation damage in graphite ex- posed to nuclear radiation, under arrangements initi- ated by F. D. Rossini of NBS with Farrington Daniels

of the Manhattan Project at the University of Chicago.

This work (unpublished) was carried out by E. J. Prosen, W. A. Eraser, J. I. Minor, Jr., W. H. Johnson,

and others. The measurements were made by combustion calorimetry. The results are of interest to coal

and coke technology because of the fact that radiation

damage results in rupturing the regular graphite struc- ture and introduces changes in the direction of the

much disordered structures of coal, coke, and char.

The effects observed in some cases amounted to as much as 1.75 kj • g~^ (21 kj • mol~^).

5. Standard Reference Materials for

Hydrocarbon Fuels

Over the years there have been developed a number

of hydrocarbons or materials needed for testing fuels.

5.1. Hydrocarbon Blends

Eight mixtures (SRM 592-599) of pure hydrocarbons representative of those occurring in hydrocarbon fuels and blending stocks are available. These

blends are primarily for use in calibrating mass spec- trometers. However, they may be useful in other spectrometric instruments or gas chromatographic techniques. They each typify either a virgin naphtha or

a catalytically cracked naphtha, and each is made up

of measured amounts by volume of five to nine hydrocarbons selected from the NBS Standard Samples of

Hydrocarbons of one of the following types: C7

paraffins, Cs paraffins, C7 cycloparaffins, Cs cycloparaffins.

5.2. Reference Fuels

Two reference fuels, n-heptane and 2,2,4-trimethylpentane (isooctane) are issued as SRM 1815 and

1816, respectively. They are intended for use by manufacturers of reference fuels for maintaining the in- tegrity of standards for knock testing of motor and

aviation fuels. They are certified as to density, refractive index, freezing point, distillation (50 percent

recovery temperature and temperature range of 80

percent minus 20 percent recovery), and zero lead

content. The purities were estimated on the basis of

freezing points and chromatographic analysis.

5.3. Lead in Reference Fuels

Three reference fuels (SRM 1636, 1637, 1638) are intended for use in calibration of instruments and

techniques for the analysis of lead in gasoline. The

samples consist of 12 ampoules of a material with accurately measured lead concentration in one of the nominal ranges of lead content, 0.03, 0.05, 0.07, and 2.0

g

• gal~i (about 8, 13, 18, and 53 mg • dm'^ respectively). The three reference materials differ in the

distribution of ampoules containing the four lead

concentrations.

5.4. Sulfur in Fuel Oil

Four reference materials are intended as analytical

standards in the determination of sulfur in fuel oils. They are commercially available oils containing sulfur

in varying amounts. The sulfur contents are certified.

The sulfur was determined as sulfate after combustion

in an oxygen bomb reaction. Three of the samples

(SRM 1621, 1622, 1623) are residual fuel oils, con- taining sulfur/ wt percent, 1.05 ±0.02; 2.15 ±0.01,

and 0.268 ± 0.004, respectively. One of the samples

(SRM 1624) is a distillate fuel oil containing sulfur/

wt percent, 0.211 ±0.004.

5.5. Heating Values of Hydrocarbon Fuels

(1) Methane. A special sample of pure methane was

analyzed for the Institute of Gas Technology for use

in maintaining the integrity of standards for heating

value of natural gas. The sample contains methane;

the impurities in mole percent are: ethane, 0.04±

0.02; nitrogen, 0.0017 ± 0.0004; oxygen, 0.0002 ±

0.0002; carbon dioxide, 0.006 ±0.002. Impurities were determined by mass spectrometry and gas chromatographic techniques. The heating value, in Btu

per standard cubic foot, is certified for the real gas

as 1014.9 (37.814 MJ • m-^*) on a dry basis and 997.2

(37.155 MJ • m~^) on a water saturated basis, with an

uncertainty of 0.4 (0.014 MJ • m-^)

.

(2 ) Benzoic acid. Not a hydrocarbon, benzoic acid

is specified in standard methods of test for liquid and

solid fuels as the test substance for calibrating the

bomb calorimeter used in the test. The benzoic acid

reference material (SRM 39i) is a highly purified

material having a certified energy of combustion in

13
the standard bomb process (prescribed conditions),

Af,/BVkJ • g-i is 26.434±0.003. It is recommended,

not only for tests of commercial fuels but also for

research on the combustion energies of pure substances. (3) 2,2,4-trimethylpentane. Commonly called isooctane, this reference material (SRM 217b) is certified as to energy of combustion in the standard bomb

process (prescribed conditions), Af/B°/kJ • is 47.712 ± 0.005. It is intended for use in petroleum

fuel testing to verify procedures for handling volatile

fuels.

6. Coal Reference Materials

Four reference coals are provided as standard samples for use in analysis of elements which create pollution problems when coal is burned.

6.1. Trace Mercury in Coal

Trace mercury in coal (SRM 1630) is a suitably

prepared commercially available coal, provisionally

certified to contain mercury/parts per million by

weight, 0.13. This value was obtained by neutron

activation analysis, and verified by flameless atomic

absorption spectrometry. Selenium content is also

given.

6.2. Sulfur in Coal

Sulfur in coal (SRM 1631) is three samples of lowvolatile bituminous coals suitable prepared and certi- fied to contain sulfur/percent by weight; 0.546±

0.003; 2.016±0.014; 3.020±0.008; and ash/percent

by weight; 5.00±0.02; 14.59+0.09; 6.17±0.02. The

sulfur and ash tests were supported by tests carried out

in five other laboratories. Moisture was also determined but lack of homogeneity in the determinations

prevented certification.

6.3. Trace Elements in Coal

Trace elements in coal (SRM 1632) is certified for

iron, manganese, zinc, vanadium, lead, chromium,

copper, nickel, arsenic, selenium, uranium, thallium,

cadmium, mercury, based on at least two methods of

analysis for each element. The elements are listed

above in the order of relative abundance. The abundances/jxg • g"~^ range from manganese, 40, to mercury, 0.12. For iron, abundance/fxg • g~^ is 8700.

Other elements tested but not certified were: titanium,

cobalt, silicon, thorium, beryllium, silver, tellurium.

6.4. Trace Elements in Coal Fly Ash

Trace elements in coal fly ash (SRM 1633) is certified for manganese, zinc, vanadium, lead, chromium,

copper, nickel, arsenic, uranium, selenium, cadmium,

mercury, based on at least two methods of analysis

for each element. The elements are listed above in

order of relative abundance. The relative abundances/

[ig ' g"-" range from manganese, 493, to mercury,

0.14. Other elements tested but not certified were:

potassium, strontium, rubidium, cobalt, thorium, beryllium, thallium.

7. Conclusion

In retrospect, it will be clear that the extensive

work done on hydrocarbons at the NBS has not been

covered completely in this article. For instances of

work not covered adequately in this review, we may

refer to the hydrocarbon synthesis work at the NBS

in the period 1937-1953 involving F. L. Howard, T. W. Mears, and D. B. Brooks. See, for a few references,

Cochrane's history of the National Bureau of Standards [58].

There are other aspects in which the question of

scope must be brought in: thus petroleum products

are used not only for fuel but for lubrication, and

here a whole new class of work may be brought in, as was mentioned only briefly. Similarly the combustion of fuels involves kinetics and reaction mechanisms, whole areas that have had an important impact on hydrocarbon fuels and which are not touched here.

Key names of NBS workers in these areas are 0. C. Bridgeman, H. S. White, S. A. McKee, J. D. Swindells,

W. J. Levedahl, and R. E. Ferguson.

Additional aspects of hydrocarbons used for fuel are the side effects of hydrocarbon usage: atmospheric

pollution by hydrocarbons and engine exhaust products, pollution of streams and the oceans by spillage

and the associated problems of modeling fate and

effect. None of these are touched here. In this area

the most recent work at NBS has been done by S. Wasik.

NBS has cooperated with universities, the Bureau

of Mines, Army, Navy and Air Force, NASA and in- dustrial laboratories during the past 75 years. As new

national programs emerge this cooperation is expected

to continue, as for instance in the preparation of a National Academy of Sciences report on needs for

thermodynamic data in the national energy program

(1974^1975) [60].

This historical review was started as a small part

of a review of much broader scope intended to form

a short chapter on "Seventy-five years of materials

research at NBS." It soon became apparent that if the review was to indicate fairly the scope and complexity of the NBS work on hydrocarbons related to their use as fuels, it would grow considerably beyond

the initial length planned.

A concise statement outlining a small portion of the

work was prepared and appears elsewhere as originally

planned. However, the author felt that the content of

the full review was of sufficient general interest, particularly in the light of current related problems in

national energy resources, that it should be made

public, rather than resting in the technical files. This

feeling was strengthend by the realization that the

historical path was being gradually dimmed by dis- persal of scientists having intimate knowledge of the

details. Hence, the review was completed in this form

and is published as a separate document. Though not

complete in many respects, we hope that . it presents a satisfactory broad outline of the NBS work on hydrocarbons and sufficient hints of work not covered

14
in detail to provide later historians with clues that

will enable definitive histories to be written.

The author wishes to thank F. D. Rossini, C. W.

Beckett, E. J. Prosen, D. D. Wagman, T. W. Mears,

J. R. Whetstone, D. E. DiUer, and W. K. Wilson for

reading and criticising all or portions of the manuscript and E. R. Horowitz for suggesting the review at

this time.

8. References

[1] Weaver, E. R., History of the gas chemistry section of the National Bureau of Standards, 1910-1957, manuscript, NBS Archives, Oct. 1964.

[2] Rosa, E. B., Use of gas for heat, and power testing of

gas, J. Franklin Institute 6, 157-86 (1912).

[3] Stillman, M. H., A portable cubic foot standard for gas, Nat. Bur. Stand. (U.S.), Tech. Paper 114 (1919).

[4] Anon. (McBride, R.S., Edwards, J. D., Weaver, E. R., et

al., see [11]), Standard methods of gas testing, Nat.

Bur. Stand. (U.S.), Circ. 48 (1916).

[5] Waidner, C. W. and Mueller, E. F., Industrial gas calori- metry, Nat. Bur. Stand. (U.S.), Tech. Paper 36 (Mar.

1914)

.

[6] Crittenden, E. C, An experimental study of flame stan- dards, Trans. Illuniin. Eng. Soc. 6, 413-37 (1911).

[7] Edwards, J. D., Determination of ammonia in illuminating

gas, Nat. Bur. Stand. (U.S.), Tech. Paper 34 (1919).

[8] McBride, R. S. and Weaver, E. R., Determination of sul- phur in illuminating gas, Nat. Bur. Stand. (U.S.),

Tech. Paper 20 (1913).

[9] Edwards, J. D., The determination of gas density, J. Ind. Eng. Chem. 9, 790-2 (1914).

[10] Anon. Gas calorimeter tables, Nat. Bur. Stand. (U.S.),

Circ. 65 (July 1917); Anon., Nat. Bur. Stand. (U.S.),

Circ. C147 (Mar. 1938) ; Jessup, R. S. and Weaver,

E. R., Nat. Bur. Stand. (U.S.), Circ. 464 (Mar. 1948).

[11] Jessup, R. S., The Thomas recording calorimeter, J. Res. Nat. Bur. Stand. (U.S.), 10, 99-122 (1933) RP 519.

[12] Eiseman, J. H. and Potter, E. A., Accuracy of the Cutler- Hammer recording gas calorimeter when used with

gases of high heating value, J. Res. Nat. Bur. Stand.

(U.S.), 58, 213-226 (1957) RP 1605.

[13] Rossini, F. D., The heat of formation of water, J. Res.

Nat. Bur. Stand. (U.S.), 6, 1-36 (1931) RP 259.

[14] Rossini, F. D., The heats of combustion of methane and

carbon monoxide, J. Res. Nat. Bur. Stand. (U.S.), 6, 37-50 (1931) RP 260.

[15] Armstrong, G. T., Calculation of the heating value of a sample of high purity methane for use as a reference

material, Nat. Bur. Stand. (U.S.), Tech. Note 299, 19 pp. (Dec. 1966).

[16] Armstrong, G. T., Domalski, E. S., and Minor, J. I., Jr., Standard combustion data for the fuel gas industry,

American Gas Association, Operating Section Proceedings, Atlanta, GA, 1972, pp. D-74-87. (American Gas

Association, Arlington, VA (1972).)

[17] Goodwin, R. D., The thermophysical properties of methane from 90 to 500 K at pressure to 700 bar. Nat. Bur. Stand. (U.S.), Tech. Note 653, 280 pp. (Apr. 1974).

[18] Younglove, B. A., The specific heats, Ctr and Cv of compressed and liquified methane, J. Res. Nat Bur. Stand.

(U.S.), 78A, No. 3, 401, (May-June 1974).

[19] Straty, G. C, Velocity of sound in dense fluid methane.

Cryogenic 14, 367 (1974).

[20] Straty, G. C, and Goodwin, R. D., Dielectric constants and polarizability of saturated and compressed fluid methane. Cryogenics 13, 717 ( 1973)

.

[21] Olson, J. D., The refractive indices and Lorenz-Lorentz

function of fluid methane, J. Chem. Phys. (in press, 1975).

[22] Haynes, W. M., Viscosity of saturated liquid methane,

Physica 70, 410 (1973).

[23] Hanley, H. J. M., McCarty, R. D., and Haynes, W. M.,

Equations for the viscosity and thermal conductivity

coefficients of methane, Cryogenics (in press, 1975).

[24] Hiza, M. J., Kidnay, A. J. and Miller, R. C, Equilibrium

Properties of Fluid Mixtures; A Bibliography of Cryogenic Data to 1975, ( Plenum Press, 1975 in press)

.

[25] Parrish, W. R., and Hiza, M. J., Liquid-vapor equilibria

in the nitrogen-methane system between 95 and 120 K,

Advances in Cryogenic Engineering 19, 300 (1974).

[26] Kidnay, A. J., Miller, R. C, Parrish, W. R., and Hiza,

M. J., Liquid-vapor phase equilibria in the nitrogenmethane system from 130 to 180 K, Cryogenics (in

press, 1975).

[27] ASTM-IP Petroleum Measurement Tables, (American

Society for Testing and Materials, Philadelphia, PA

1952).

[28] Bearce, H. W., and Peffer, E. L., Density and thermal

expansion of American petroleum oils, Nat. Bur. Stand.

(U.S.), Tech. Paper 77, 26 pages, (Aug. 1916).

[29] United States standard tables for petroleum oils, Nat.

Bur. Stand. (U.S.), Circ. 57, (Jan. 1916).

[30] Jessup, R. S., Compressibility and thermal expansion of petroleum oils in the range 0 to 300 °C, J. Res. Nat.

Bur. Stand. (U.S.), 5, 985-1039, (1930) RP 244.

[31] Cragoe C. S., and Hill, E. F., Thermal expansion of gasolines from 0 to 30 °C, J. Res. Nat. Bur. Stand.

(U.S.), 7, 1133-1145 (1931) RP 393.

[32] Hyams, H., and Holmes, H. R., International petroleum

tables—Their origin, development and practical importance. Third World Petroleum Congress, The Hague,

1951, Proceedings Section IX, Transport, Storage, and

Distribution, pp. 68-81. (E. J. Brill, Leiden, 1951).

[33] Hill, A. H., Simpson, J. A., and Whetstone, J. R., Investi- gation of densities and thermal expansion coefiicients applicable to petroleum measurement. Preprint manuscript, April 1975.

[34] Cragoe, C. S. Thermal properties of petroleum products,

Nat Bur. Stand. (U.S.), Misc. Publ. 97, 48 pages, (Nov. 1929).

References [30], [31], and [34] bear the following footnote: This paper contains results obtained in an investigation of "The Thermodynamic Properties of Petroleum Hydrocarbons"

listed as Project No. 38 of American Petroleum Institute Research. Financial assistance in this work has been received

from a research fund of the American Petroleum Institute donated by John D. Rockefeller. This fund is administered by

the institute with the cooperation of the Central Petroleum

Committee of the National Research Council.

[35] Armstrong, G. T., Fano, L., Jessup, R. S., Marantz, S., Mears, T. W., and Walker, J. A., Net heat of combustion and other properties of kerosine and related

fuels, J. Chem. Eng. Data 7, 107-111 (1962).

[36] American Society for Testing and Materials (Committee

D-2 on Petroleum Products and Lubricants), Standard

method for estimation of net heat of combustion of aviation fuels (ASTM Designation D-1405), 1972 Annual Book of ASTM Standards, Part 17, pp. 514-522.

[37] Rossini, F. D., Mair, B. J., and StreiS, A. J., Hydrocarbons from Petroleum, Am. Chem. Soc. Monograph

No. 121. (Reinhold Publishing Corp., New York, 1953),

556 -|- xvi pp.

[38] Prosen, E. J., and Rossini, F. D., Heats of combustion of eight normal paraffin hydrocarbons in the liquid state,

J. Res. Nat. Bur. Stand. (U.S.), 33, 255-272, (1944)

RP 1607.

[39] Dickinson, H. C, Combustion calorimetry and the heats

of combustion of cane sugar, benzoic acid, and naphthalene, Nat. Bur. Stand. (U.S.), Sci. Paper 230, 189- 257, (1914).

[40] Rossini, F. D., Experimental Thermochemistry (Interscience Publishers, Inc., New York, 1956)

.

(a) Coops, J., Jessup, R. S., and van Nes, K., Calibration of calorimeters for reaction in a bomb at constant volume. Chapter 3, pp. 27-58.

15
(b) Rossini, F. D., Calibration of calorimeters for re- actions in a flame at constant pressure, Chapter

4, pp. 59-74.

(c) Prosen, E. J., Combustion in a bomb of com- pounds containing carbon, hydrogen, oxygen, and

nitrogen. Chapter 6, pp. 129-148.

[41] Washburn, E. W., Standard states for bomb calorimetry,

J. Res. Nat. Bur. Stand. (U.S.), 10, 525 (1933) RP 546.

[42] Jessun, R. S., Precise measurement of heat of combustion

with a bomb calorimeter, Nat. Bur. Stand. (U.S.),

Monogr. 7, 23 pages (Feb. 1960).

[43] American Society for Testing and Materials (Committee

D-2 on Petroleum Products), Heat of combustion of hydrocarbon fuels by bomb calorimeter (high-precision

method), ASTM Designation: D-2382, ASTM Book of Standards (1965 ff). [44] Rossini, F. D., Pitzer, K. S., Taylor, W. J., Ebert, J. P., Kilpatrick, J. E., Beckett, C. W., Williams, M. G., Werner, H. G., Selected values of properties of hydrocarbons, Nat. Bur. Stand. (U.S.), C461 (1947).

[45] Prosen, E. J., Pitzer, K. S., and Rossini, F. D., Free

energies and equilibria of isomerization of the 18 oc- tanes, J. Res. Nat. Bur. Stand. (U.S.), 34, 255-261 (1945) RP 1641.

[46] Kilpatrick, J. E., Beckett, C. W., Prosen, E. J., Pitzer, K. S., and Rossini, F. D., Heats, Equilibrium constants and free energies of formation of the Cs to Cs

diolefins, styrene, and the methylstyrenes, J. Res. Nat. Bur. Stand. (U.S.), 42. 22.5-239 (1949) RP 1964.

[47] Kilpatrick, J. E., and Pitzer, K. S., Normal coordinate

analysis of the vibrational frequencies of ethylene, pro- pylene, cis-2-butene, trans-2-butene, and isobutene, J. Res. Nat. Bur. Stand. (U.S.), 38. 191-209 (1947)

RP 1768.

[48a] Prosen, E. .1., and Rossini, F. D., Heats of combustion and formation of the paraffin hydrocarbons at 25 °C. J. Res. Nat. Bur. Stand. (U.S.), 34, 263-269

(1945) RP 1642. [48b] Taylor, W. J.. Pignocco. J. M.. and Rossini, F. D.. Method for calculating the properties of hydrocarbons

and its application to the refractive indices, densities,

and boiling points of the paraffin and mono-olefin

hydrocarbons, J. Res. Nat. Bur. Stand. (U.S.), 34,

413-434 (1945) RP 1651.

[49] Pitzer K. S., and Beckett, C. W., Tautomerism in cyclohexane derivatives; reassignment of configuration of the 1,3-dimethylcyclohexanes, J. Am. Chem. Soc. 69,

977 (1947).

[50] Prosen, E. J., Johnson, W. H., and Rossini, F. D., Heats

of formation and isomerization of the eight CsHia alkylcyclohexanes in the liquid and gaseous states, J. Res.

Nat. Bur. Stand. (U.S.), 39. 173-175 (1947) RP 1821.

[51a] West, E. D., and Ishihara, S., A. calorimetric determination of the enthalpy of graphite from 1200 to 2600 K. Advances in thermophysical properties at extreme

temperatures and pressures (American Society of Mechanical Engineers. New York, 1965). See also NBS

Special Publication 300, Vol. 6, Heat, 1970.

[51b] Cezairliyan. A. Measurement of the heat capacity of graphite in the range 1500 to 3000 K by a pulse heating

method. Proceedings of the Sixth Symposium on Thermophysical Properties. P. E. Liley, ed., (Am. Soc. Mech.

Eng., New York, 1973).

[52a] Jessup, R. S., Heats of combustion of diamond and of graphite, J. Res. Nat. Bur. Stand. (U.S.), 21, 475-490

(1938) RP 1140.

[52b] Prosen, E. J., and Rossini, F. D., Some experimental

data on the heats of combustion of benzoic ac'd and

carbon (graphite), J. Res. Nat. Bur. Stand. (U.S.),

33. 439 (1944) RP 1619.

[53] Dewey, P. H., and Harper, D. R., 3rd., Heats of combustion of anthracite cokes and of artificial and natural

graphites, J. Res. Nat. Bur. Stand. (U.S.), 21, 457-474

(1938) RP 1139.

[54] Rossini, F. D., and Jessup, R. S. Heat and free energy of formation of carbon dioxide and of the transition be- tween graphite and diamond J. Res. Nat. Bur. Stand.

(U.S.), 21, 491-513 (1938) RP 1141.

[55] Wagman, D. D., Kilpatrick, J. E., Taylor, W. J., Pitzer, K. S., and Rossini, F. D., Heats, free energies, and

equilibrium constants of some reactions involving O2, Ha, HoO, C, CO, CO2, and CH4. J. Res. Nat. Bur. Stand.

(U.S.), 34, 143-161 (1945) RP 1634.

[56] Wagman, D. D., Evans, W. H., Parker, V. B., Halow, I., Bailey, S. M., and Schumm, R. H., Selected values of chemical thermodynamic properties, Nat. Bur. Stand.

(U.S.), Tech. Note 270-3, 268 pages, (Jan. 1968).

[57] Sunner, S., et al., CODATA recommended key values

for thermodynamics, 1973, CODATA Bulletin No. 10

(ICSU CODATA Frankfurt/Main, Germany, December, 1973).

[58] Cochrane, R. C, Measures for Progress: A History of the National Bureau of Standards, Nat. Bur. Stand.

(U.S.), Misc. Publ. 275, 728 pages, (1966). See especially pp. 185, 266-7, 369, 374, 419-420, 464, 466.

[59] Bichowsky, F. R., and Rossini, F. D., Thermochemistry

of the chemical substances, (Reinhold Publishing Corp.,

New York, NY, 1936).

[60] National Academy of Sciences, Report of the Conference

on Thermodynamics and National Energy Problems,

June 10-12, 1974. Warrenton, VA (National Academy

of Sciences, Washington, DC, 1974).

[61] Anon., War Work of the Bureau of Standards, Nat. Bur. Stand. (U.S.), Misc. Publ. 46, (1921). (a) pp. 23-24, aviation gasoline; (b) pp. 179-183, natural gas; (c) pp. 291-293, toluene recovery.

[62] Cragoe, C. S., unpublished work. See, for instance: Inter- national Critical Tables (E. W. Washburn, ed.), Vol. V (1929). Vapor pressure tables.

[63] Armstrong, G. T., Brickwedde, F. G., and Scott, R. B.: (a) The vapor pressures of the deuteromethanes, J. Chem.

Phys. 21, 1297-8 (1953); (b) Vapor pressures of the methanes, J. Res. Nat. Bur. Stand. (U.S.), 55, 39-52 (1955) RP 2603.

[64] Urey, H. C, Brickwedde, F. G., and Murphy, G. M., A

hydrogen isotope of mass 2. Phys. Rev. 39, 164-165 (1932) ; 40, 1-15 (1932).

[65] Domalski, E. S., Selected values of heats of combustion

and heats of formation of organic compounds containing the elements C, H, N, O, P, and S. J. Phys.

Chem. Ref. Data 1, 221-277 (1972).

[66] Kharasch, M. S. Heats of combustion of organic compounds, J. Res. Nat Bur. Stand. (U.S.), 2, 359 (1929)

RP 41.

16
H8^-114A (REV. 7-73)

L'.S. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET

1. PUBLICATION OR REPORT NO.

NBS SP-434

2. Gov't Accession

No.

3. Recipient's Accession No.

4. TITLE AND SUBTITLE

Hydrocarbons for Fuel - 75 Years of Research at NBS

5. Publication Date May 1976

6. Performing Organization Code

7. AUTHOR(S)

George T. Armstrong

8. Performing Organ. Report No.

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

10. Project/Task/Work Unit No. 3161112

11. Contract/Grant No.

12. Sponsoring Organization Name and Complete Address (Street, City, State, ZIP) 13. Type of Report & Period

Covered

Final

14. Sponsoring Agency Code

15. SUPPLEMENTARY NOTES

Library of Congress Catalog Card Number: 75-619428

,16. ABSTRACT (A 200-word or less {actual summary o( most si^ificant information. If document includes a significant

\ bibliography or literature survey, mention it here.)

In this historical review the NBS work on hydrocarbons is discussed in terms of the

three major classes of natural hydrocarbonaceous fuels: natural gas, petroleum,

; and coal. The work done on the measurement of properties of the pure components

i has included measurement of the values of the properties themselves and development

of practical and accurate measurement procedures and instruments. In addition,

combustion energies, densities, viscosities, vapor pressures, refractive indices,

elemental compositions and other parameters have been determined for complex fuel

mixtures and correlated to find methods of estimating properties. Extensive

standard reference data tables have been compiled and a number of standard

reference materials have been developed.

17. KEY WORDS (six to twelve entries; alphabetical order; capitalize only the first letter of the first key word unless a proper name; separated by semicolons) ^oal ; energy; fuel; graphite; hydrocarbons; metering; methane;

natural gas; petroleum; physical properties; standard reference materials.

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activity. Explores power for industrial needs and competition between the utilities and

general industry for the same

materials in short supply.

5. What the comparable energy problem is for the rest of

Order your complete energy set now for $35 and save.

Mail lo: The National Technical Information Service

U.S. DEPARTMENT OF COMMERCE, Springfield, Va. 22161 Q Send me the complete three-volume set. The U.S. Energy Problem, PB-207 517-SET/PSW.

$35 $43) Send me only

Summary of The U.S. Energy Problem, Vol. I, PB-207 517/PSW. $4.75 (foreign $7.25) Q Appendices A through C including Energy Status, Cost Trade Off Analysis, Residential Energy Analysis, Nuclear Energy, 53 figures and tables. Vol. II, Part A, PB-207 518/PSW.

$17.25 (foreign $19.75) Q Appendices H through U including Off-Peak Power Storage Systems, Electrochemical R&D,

Transportation, Energy & Environment, Energy-Related Minerals, more than 100 figures and

tables. Vol. II, Part B, PB-207 519/PSW. $15.25 (foreign $17.75) Q Also send me the free NTIS Information Services booklet, NTIS-PR-154. Charge my NTIS Deposit Account No, Q Bill me (not applicable to foreign customers). Add $5 per order. Q Here is my check for

NAME

TITLE .ORGANIZATION.

ADDRESS.

CITY .STATE. ZIP

the world with detailed energy

and economic data for most

of the world's countries. How

the absence of capital will affect world power problems.

6. How technological variables

affect electrical energy. In- depth analysis of the effect of

each technological variable on

energy cost. Tables and illustrative examples to make your

own estimates for cost/benefit

ratios. Explains how to compare unit cost with research

cost.

7. Why the Nation must ur- gently analyze the alternatives.

And move to establish a national power grid.

8. Which of the solar energy

conversion and direct energy

conversion proposals merit future research and development.

9. Where more R&D is needed

for domestic energy consumption. Investigates possible re- covery and minimum waste of

domestic energy consumption.

10. How the development of

practical nuclear breeder re- actor systems can save $100

billion—if developed by 1985

rather than 1990. Clear explanations of the various concepts with a review of the

principles and facts related to

the use of nuclear fuels.
WasWhen

/Was

...but that's all changed now.

Today, increased energy costs—caused by in- creasing demand—boost tlie price of consumer

goods, fuel inflation, and hurt our balance of

payments.

That's why conserving energy is a must today,

especially for you in the business and industry

community which uses two thirds of our nation's

energy.

Now . . . there's a book to tell you how to do

it. It's called EPIC—the Energy Conservation

Program Guide for Industry and Commerce. Pre- pared for you by the Commerce Department's

National Bureau of Standards in cooperation

with the Federal Energy Administration.

EPIC is a comprehensive handbook that can

help you establish or improve an energy conservation program in your organization.

Not only industry and commerce but also hospitals, universities, research institutes, ANY or- ganization that uses energy—and has to pay

the bills—will want a copy of EPIC.

EPIC outlines in detail the steps in setting up

an energy conservation program.

It contains a checklist of more than 200 Energy

Conservation Opportunities—suggestions to save

U.S. DEPARTMENT OF COMMERCE / National

energy in a dozen different areas. EPIC'S actual case histories of energy saving

actions help you estimate your potential for saving energy—and reducing costs. And EPIC contains much more—financial analysis procedures to evaluate projects, sources of

information on energy conservation, engineering

data and factors, an energy conservation bib- liography.

Make EPIC part of your plan to control energy

use and costs. Make EPIC part of your contribution to using energy resources wisely ... so we can keep America working and growing.

To order your copy of EPIC, send $2.50 per

copy (check, money order or Superintendent of _ Documents Coupons) to Superintendent of Documents, U.S. Government Printing Office,

Washington, D.C. 20402.

Ask for NBS Handbook

115, EPIC, 013.11:115.

Discount of 25% on

orders of 100 copies or more.

BStCT CtMSBtVATKN

'

, t , PTOGRAK GUmE FOR mausTvi mo fn—niif

Bureau of Standards

FEDERAL ENERGY ADMINISTRATION / Conservation and Environment

6 U. S. GOVERNMENT PRINTING OFFICE : 1976—210-801/273
NBS TECHNICAL PUBLICATIONS

PERIODICALS JOURNAL OF RESEARCH reports National Bureau

of Standards research and development in physics,

mathematics, and chemistry. It is published in two sections, available separately:

• Physics and ChemiBtry (Section A)

Papers of interest primarily to scientists working in these fields. This section covers a broad range of physical and chemical research, with major emphasis on

standards of physical measurement, fundamental constants, and properties of matter. Issued six times a

year. Annual subscription: Domestic, $17.00; Foreign,

$21.25.

• Mathematical Sciences (Section B)

Studies and compilations designed mainly for the mathematician and theoretical physicist. Topics in mathematical statistics, theory of experiment design, numerical analysis, theoretical physics and chemistry, logical

design and programming of computers and computer

systems. Short numerical tables. Issued quarterly. Annual subscription: Domestic, $9.00; Foreign, $11.25.

DIMENSIONS/NBS (formerly Technical News Bulletin) —This monthly magazine is published to inform

scientists, engineers, businessmen, industry, teachers,

students, and consumers of the latest advances in science and technology, with primary emphasis on the work at NBS. The magazine highlights and reviews such

issues as energy research, fire protection, building tech- nology, metric conversion, pollution abatement, health and safety, and consumer product performance. In addition, it reports the results of Bureau programs in measurement standards and techniques, properties of matter and materials, engineering standards and services, instrumentation, and automatic data processing.

Annual subscription: Domestic, $9.45; Foreign, $11.85.

NONPERIODICALS

Monographs—Major contributions to the technical liter- ature on various subjects related to the Bureau's scientific and technical activities.

Handbooks—Recommended codes of engineering and

industrial practice (including safety codes) developed

in cooperation with interested industries, professional

organizations, and regulatory bodies.

Special Publications—Include proceedings of confer- ences sponsored by NBS, NBS annual reports, and other

special publications appropriate to this grouping such

as wall charts, pocket cards, and bibliographies.

Applied Mathematics Series—Mathematical tables,

manuals, and studies of special interest to physicists,

engineers, chemists, biologists, mathematicians, computer programmers, and others engaged in scientific and technical work.

National Standard Reference Data Series—Provides

quantitative data on the physical and chemical properties of materials, compiled from the world's literature and critically evaluated. Developed under a world-wide

program coordinated by NBS. Program under authority

of National Standard Data Act (Public Law 90-396).

NOTE: At present the principal publication outlet for

these data is the Journal of Physical and Chemical

Reference Data (JPCRD) published quarterly for NBS

by the American Chemical Society (AC;S) and the American Institute of Physics (AIP). Subscriptions, reprints,

and supplements available from ACS, 1155 Sixteenth

St. N. W., Wash. D. C. 20056.

Building Science Series—Disseminates technical infor- mation developed at the Bureau on building materials,

components, systems, and whole structures. The series presents research results, test methods, and performance criteria related to the structural and environmental functions and the durability and safety characteristics of building elements and systems.

Technical Notes—Studies or reports which are complete

in themselves but restrictive in their treatment of a

subject. Analogous to monographs but not so comprehensive in scope or definitive in treatment of the subject area. Often serve as a vehicle for final reports of work performed at NBS under the sponsorship of other

government agencies.

Voluntary Product Standards—Developed under pro- cedures published by the Department of Commerce in Part 10, Title 15, of the Code of Federal Regulations.

The purpose of the standards is to establish nationally

recognized requirements for products, and to provide

all concerned interests with a basis for common understanding of the characteristics of the products. NBS

administers this program as a supplement to the activities of the private sector standardizing organizations.

Federal Information Processing Standards Publications

(FIPS PUBS)—Publications in this series collectively constitute the Federal Information Processing Standards Register. Register serves as the official source of information in the Federal Government regarding stand- ards issued by NBS pursuant to the Federal Property

and Administrative Services Act of 1949 as amended.

Public Law 89-306 (79 Stat. 1127), and as implemented

by Executive Order 11717 (38 FR 12315, dated May 11, 1973) and Part 6 of Title 15 CFR (Code of Federal

Regulations)

.

Consumer Information Series—Practical information,

based on NBS research and experience, covering areas

of interest to the consumer. Easily understandable

language and illustrations provide useful background

knowledge for shopping in today's technological

marketplace.

NBS Interagency Reports (NBSIR) —A special series of interim or final reports on work performed by NBS for

outside sponsors (both government and non-government). In general, initial distribution is handled by the sponsor; public distribution is by the National Technical

Information Service (Springfield, Va. 22161) in paper

copy or microfiche form.

Order NBS publications (except NBSIR's and Biblio- graphic Subscription Services) from: Superintendent of Documents, Government Printing Office, Washington,

D.C. 20402. BIBLIOGRAPHIC SUBSCRIPTION SERVICES

The following current-awareness and literature-survey

bibliographies are issued periodically by the Bureau:

Cryogenic Data (Center Current Awareness Service

A literature survey issued biweekly. Annual subscription: Domestic, $20.00; foreign, $25.00.

Liquefied Natural Gas. A literature survey issued quarterly. Annual subscription: $20.00.

Superconducting Devices and Materials. A literature

survey issued quarterly. Annual subscription : $20.00.

Send subscription orders and remittances for the

preceding bibliogi-aphic services to National Bureau of Standards, Cryogenic Data Center (275.02)

Boulder, Colorado 80302.

Electromagnetic Metrology Current Awareness Service

Issued monthly. Annual subscription: $24.00. Send

subscription order and remittance to Electromagnetics

Division, National Bureau of Standards, Boulder,

Colo. 80302.
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