JV) NBS SPECIAL PUBLICATION 434 Vau of U.S. DEPARTMENT OF COMMERCE / National Bureau of Standards ydrocarbons for Fuel- 75 Years of Materials Research at NBS C NATIONAL BUREAU OF STANDARDS The National Bureau of Standards^ was established by an act of Congress March 3, 1901. The Bureau's overall goal is to strengthen and advance the Nation's science and technology and facilitate their effective application for public benefit. To this end, the Bureau conducts research and provides: (1) a basis for the Nation's physical measurement system, (2) scientific and technological services for industry and government, (3) a technical basis for equity in trade, and (4) technical services to promote public safety. The Bureau consists of the Institute for Basic Standards, the Institute for Materials Research, the Institute for Applied Technology, the Institute for Computer Sciences and Technology, and the Office for Information Programs. THE INSTITUTE FOR BASIC STANDARDS provides the central basis within the United States of a complete and consistent system of physical measurement; coordinates that system with measurement systems of other nations; and furnishes essential services leading to accurate and uniform physical measurements throughout the Nation's scientific community, industry, and commerce. The Institute consists of the Office of Measurement Services, the Office of Radiation Measurement and the following Center and divisions: 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 materials needed by industry, commerce, educational institutions, and Government; provides advisory and research services to other Government agencies; and develops, produces, and distributes standard reference materials. The Institute consists of the Office of Standard Reference Materials, the Office of Air and Water Measurement, and the following divisions: Analytical Chemistry — Polymers — Metallurgy — Inorganic Materials — Reactor Radiation — Physical Chemistry. THE INSTITUTE FOR APPLIED TECHNOLOGY provides technical services to promote the use of available technology and to facilitate technological innovation in industry and Government; cooperates with public and private organizations leading to the development of technological standards (including mandatory safety standards), codes and methods of test; and provides technical advice and services to Government agencies upon request. The Insti- tute consists of the following divisions and Centers: Standards Application and Analysis — Electronic Technology — Center for Consumer Product Technology: Product Systems Analysis; Product Engineering — Center for Building Technology: Structures, Materials, and Life Safety; Building Environment; Technical Evalua- tion and Application — Center for Fire Research: Fire Science; Fire Safety Engineering. THE INSTITUTE FOR COMPUTER SCIENCES AND TECHNOLOGY conducts research and provides, technical services designed to aid Government agencies in improving cost effec- tiveness in the conduct of their programs through the selection, acquisition, and effective utilization of automatic data processing equipment; and serves as the principal focus within the executive branch for the development of Federal standards for automatic data processing equipment, techniques, and computer languages. The Institute consists of the following divisions: Computer Services — Systems and Software — Computer Systems Engineering — Informa- tion Technology. THE OFFICE FOR INFORMATION PROGRAMS promotes optimum dissemination and accessibility of scientific information generated within NBS and other agencies of the Federal Government; promotes the development of the National Standard Reference Data System and a system of information analysis centers dealing with the broader aspects of the National Measurement System; provides appropriate services to ensure that the NBS staff has optimum accessibility to the scientific information of the world. The Office consists of the following organizational units: Office of Standard Reference Data — Office of Information Activities — Office of Technical Publications — Library — Office of International Relations — Office of International Standards. 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 Fuel- 75 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 (Order by SD Catalog No. C13.10:434). Price 55 cents. (Add 25 percent additional for other than U.S. mailing). 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 pres- sures, 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 domestic heating and cooking fuel, its prior use hav- ing been mainly for illumination. Early NBS work The scope of NBS work on hydrocarbons for fuels was directed to the goals of safety and quality in this over ihe years is so broad and complex that a brief new fuel, and to measurement of its properties. Studies review such as this can only point out highlights. Let included methods of measurement of gas quantities us briefly outline first of the principal features some (volumetrically ) and of density, measurement of heat- of the NBS fuel hydrocarbons work. ing value and candlepower, and determination of More or less broad coverage has been given to all impurities. Circulars were prepared describing how the fossil fuels. The work has covered natural gas and these could be determined accurately. For the States petroleum more extensively than coal; however, even the NBS also tested calorimeters for measuring the here some interesting and perhaps little appreciated heating value of gaseous fuels. In later years NBS work has been done. In each of these areas the prac- evaluated automatic calorimeters for continuous re- tical fuels themselves have been studied, as well as cording of gas heating values. well-characterized substances of which they are com- One important result of NBS work has been the posed. Significant effort