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M alilla 011

6th Edition
A, W, Drews, editor

Manual on Hydrocarbon

Analysis: 6th Edition


A. W. Drews
editor

ASTM Manual Series: MNL3 ASTM Stock #: MNL3

100 Barr Harbor Drive, West Conshohocken, PA 19428-2959

Library of Congress Cataloging-in-Publication Data Manual on hydrocarbon analysis--6th ed./A. W. Drews, editor (ASTM manual series: MNL 3) ASTM Stock #: MNL3 Includes bibliographical references and index ISBN 0-8031-2080-X 1. Petroleum productswAnalysis. 2. Hydrocarbons--Analysis. I. Drews, A.W. II. Series. TP691.M358 1998 665.5---dc21 98-25886 CIP

Copyright 1998 by the AMERICAN SOCIETY FOR TESTING AND MATERIALS, West Conshohocken, PA. All rights reserved. This material may not be reproducedor copied, in whole or in part, in any printed, mechanical, electronic, film, or other distribution and storage media, without the written consent of the publisher.

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NOTE: This manual does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this manual to establish appropriate safety and health practices and determine the applicability of regulatory limitations pnor to use.

NOTE: The Society is not responsible, as a body, for the statements and opinions advanced in this publication.

Printed in Baltimore June 1998

Foreword
THIS SIXTHEDITIONOF THE Manual on Hydrocarbon Analysis, sponsored by ASTM Committee D02 on Petroleum Products and Lubricants, has been expanded even further than the fifth edition. First appearing in 1963 as STP332, this manual was updated by Committee D02 in 1968, 1977, 1987, and 1992. In this 1998 edition, Part 2 has been expanded to include 26 additional ASTM test methods. Furthermore, the number of chapters has been increased from five to seven through the creation of a separate chapter, "Analysis of Kerosine, Diesel and Aviation Turbine Fuels," and a totally new chapter, "Analysis of Waxes." For additional information on the significance of tests, the reader is encouraged to consult the Industry and governmental requirements for accurate, more detailed data in a shorter time frame have resulted in substantial method changes. Rapid instrumental techniques, incorporating automatic sampling and on-line instrumentation, are replacing many of the time-honored empirical and, even, wet-chemical procedures. Yet many of the established techniques are still utilized and, thus, they are included in this manual along with the methods that are replacing them. It is exciting to speculate what further changes will occur before issuance of the next edition. Publication of this manual would not have been possible without the efforts of the ASTM staff, the authors--N. G. Johansen, J. M. McCann, G. Hemighaus, T. M. Warne, A. J. Lubeck, A. D. Barker, C.H. Pfeiffer, the reviewers--S. E. Litka and N. D. Smith, and to L. A. Drews for collating, formatting, and reviewing the texts. I express my appreciation to all those who made this sixth edition a reality. A. W. Drews, editor Subcommittee D02.04 on Hydrocarbon Analysis

Manual on Significance of Tests for Petroleum Products, 6th Edition.


Methodology is changing quickly, requiring revisions to existing methods and the standardization of new ones. The impact of computerization and microprocessors cannot be overemphasized. Modern data-handling capabilities allow highly detailed compositional analyses to be performed that were once only a vision. Some of these resulting methods have been standardized; others will follow rapidly as experience is gained.

ool

Ul

Purpose of Manual
THE PURPOSEOF THIS MANUALis two-fold. The seven imroductory chapters provide the analyst with a comprehensive overview of current practices and tests relating to the analysis of hydrocarbons. The accompanying collection of ASTM test methods furnishes a convenient reference within a single volume. It is hoped that this combination will provide the reader with a clearer understanding and appreciation of this diversified subject.

iv

Contents
INTRODUCTORY INFORMATION

Introduction Table 1--Summary of Product Types Produced from Petroleum Table 2--Summary of ASTM Test Methods (by subject) Table 3--Number of Isomeric Paraffins Table 4--Summary of Hydrocarbon Types in Petroleum Fractions

3 4 5 11 11

PART 1--DISCUSSIONOF ANALYSES BY PRODUCT TYPE Analysis of Cs and Lighter Hydrocarbons by N. G. J o h a n s e n Introduction Current Practices Future Trends
2 Analysis of Gasoline a n d Other Light Distillate Fuels by J. M. M c C a n n Introduction Current Practices Future Trends 15 15 15 16 18 18 18 20

Analysis o f Kerosine, Diesel, a n d Aviation T u r b i n e Fuel by G. H e m i g h a u s Introduction Current Practices Future Trends
4 Analysis of Viscous Oils by T. M. W a r n e Introduction Current Practices Future Trends

22 22 22 23 25 25 25 30 31 31 31 32 34 34 35 39 41 41 41 42

Analysis o f Waxes by A. D. B a r k e r Introduction Current Practices Future Trends 6 Analysis o f Crude Otis by A. J. L u b e c k Introduction Current Practices Future Trends Analysis o f A r o m a t i c Hydrocarbons by C. H. P f e i f f e r Introduction Current Practices Future Trends
V

vi

CONTENTS
PART 2 - - A S T M TEST METHODS

The test methods in this section are arranged in alphanumeric sequence. The page numbers apply only to this manual and not to the standard documents as they appear in the annual ASTM Book of Standards. See Table 2 for a list of test methods by subject. The following is a list of all test methods included in Part 2. It includes all test methods referenced in the seven chapters except as indicated in the chapters. It does not include all of the test methods cited in Table 2. D5 D36 D56 D86 D87 D96 D97 D127 D130 D 189 D287 D323 D341 D445 D447 D473 D482 D524 D611 D664 D721 D848 D849 D850 D852 D853 D972 D976 D 1078 D1133 D 1142 D 1159 Dl160 D 1209 D1218 D1250 D1265 D1298 D1319 D1322 D1492 D1552 D1685 D1747 D1840 Test Method for Penetration of Bituminous Materials Test Method for Softening Point of Bitumen (Ring-and-Ball Apparatus) Test Method for Flash Point by Tag Closed Tester Test Method for Distillation of Petroleum Products at Atmospheric Pressure Test Method for Melting Point of Petroleum Wax (Cooling Curve) Test Method for Water and Sediment in Crude Oil by Centrifuge Method (Field Procedure) Test Method for Pour Point of Petroleum Oils Test Method for Drop Melting Point of Petroleum Wax Including Petrolatum Test Method for Detection of Copper Corrosion from Petroleum Products by the Copper Strip Tarnish Test Test Method for Conradson Carbon Residue of Petroleum Products Test Method for API Gravity of Crude Petroleum and Petroleum Products (Hydrometer Method) Test Method for Vapor Pressure of Petroleum Products (Reid Method) Viscosity-Temperature Charts for Liquid Petroleum Products Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity) Test Method for Distillation of Plant Spray Oils Test Method for Sediment in Crude Oils and Fuels Oils by the Extraction Method Test Method for Ash from Petroleum Products Test Method for Ramsbottom Carbon Residue of Petroleum Products Test Methods for Aniline Point and Mixed Aniline Point of Petroleum Products and Hydrocarbon Solvents Test Method for Acid Number of Petroleum Products by Potentiometric Titration Test Method for Oil Content of Petroleum Waxes Test Method for Acid Wash Color of Industrial Aromatic Hydrocarbons Test Method for Copper Strip Corrosion of Industrial Aromatic Hydrocarbons Test Method for Distillation of Industrial Aromatic Hydrocarbons and Related Materials Test Method for Solidification Point of Benzene Test Method for Hydrogen Sulfide and Sulfur Dioxide Content (Qualitative) of Industrial Aromatic Hydrocarbons Test Method for Evaporation Loss of Lubricating Greases and Oils Test Method for Calculated Cetane Index of Distillate Fuels Test Method for Distillation Range of Volatile Organic Liquids Test Method for Kauri-Butanol Value of Hydrocarbon Solvents Test Method for Water Vapor Content of Gaseous Fuels by Measurement of Dew-Point Temperature Test Method for Bromine Number of Petroleum Distillates and Commercial Aliphatic Olefins by Electrometric Titration Test Method for Distillation of Petroleum Products at Reduced Pressure Test Method for Color of Clear Liquids (Platinum-Cobalt Scale) Test Method for Refractive Index and Refractive Dispersion of Hydrocarbon Liquids Guide for Petroleum Measurement Tables Practice for Sampling Liquefied Petroleum (LP) Gases (Manual Method) Practice for Density, Relative Density (Specific Gravity) or API Gravity of Crude Petroleum and Liquid Petroleum Products by Hydrometer Method Test Method for Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption Test Method for Smoke Point of Aviation Turbine Fuels Test Method for Bromine Index of Aromatic Hydrocarbons by Coulometric Titration Test Method for Sulfur in Petroleum Products (High-Temperature Method) Test Method for Traces of Thiophene in Benzene by Spectrophotometry Test Method for Refractive Index of Viscous Materials Test Method for Naphthalene Hydrocarbons in Aviation Turbine Fuels by Ultra Violet Spectrophotometry 47 50 54 64 77 80 87 95 97 103 109 112 120 126 134 137 141 144 152 159 166 172 175 177 182 184 186 190 193 200 202 213 222 240 243 247 249 252 257 263 269 272 277 280 284

CONTENTS
D1945 D1946 D1988 D2007 D2158 D2163 D2171 D2306 D2360 D2386 D2425 D2426 D2500 D2501 D2502 D2503 D2504 D2505 D2549 D2593 D2597 D2622 D2650 D2710 D2712 D2784 D2786 D2878 D2887 D2892 D3054 D3120 D3205 D3227 D3230 D3235 D3239 D3241 D3246 D3279 D3524 D3606 D3700 D3701 Test Method for Analysis of Natural Gas by Gas Chromatography Practice for Analysis of Reformed Gas by Gas Chromatography Test Method for Mercaptans in Natural Gas Using Length-of-Stain Detector Tubes Test Method for Characteristic Groups in Rubber Extender and Processing Oils and Other Petroleum-Derived Oils by Clay-Gel Absorption Chromatographic Method Test Method for Residues in Liquefied Petroleum (LP) Gases Test Method for Analysis of Liquefied Petroleum (LP) Gases and Propene Concentrates by Gas Chromatography Test Method for Viscosity of Asphalts by Vacuum Capillary Viscometer Test Method for C8 Aromatic Hydrocarbon Analysis by Gas Chromatography Test Method for Trace Impurities in Monocyclic Aromatic Hydrocarbons by Gas Chromatography Test Method for Freezing Point of Aviation Fuels Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry Test Method for Butadiene Dimer and Styrene in Butadiene Concentrates by Gas Chromatography Test Method for Cloud Point of Petroleum Oils Test Method for Calculation of Viscosity-Gravity Constant (VGC) of Petroleum Oils Test Method for Estimation of Molecular Weight (Relative Molecular Mass) of Petroleum Oils from Viscosity Measurements Test Method for Relative Molecular Mass (Molecular Weight) of Hydrocarbons by Thermoelectric Measurement of Vapor Pressure Test Method for Noncondensable Gases in C2 and Lighter Hydrocarbon Products by Gas Chromatography Test Method for Ethylene, Other Hydrocarbons, and Carbon Dioxide in High-Purity Ethylene by Gas Chromatography Test Method for Separation of Representative Aromatics and Nonaromatics Fractions of High Boiling Oils by Elution Chromatography Test Method for Butadiene Purity and Hydrocarbon Impurities by Gas Chromatography Test Method for Analysis of Demethanized Hydrocarbon Liquid Mixtures Containing Nitrogen and Carbon Dioxide by Gas Chromatography Test Method for Sulfur in Petroleum Products by X-Ray Spectrometry Test Method for Chemical Composition of Gases by Mass Spectrometry Test Method for Bromine Index of Petroleum Hydrocarbons by Electrometric Titration Test Method for Hydrocarbon Traces in Propylene Concentrates by Gas Chromatography Test Method for Sulfur in Liquefied Petroleum Gases (Oxy-Hydrogen Burner or Lamp) Test Method for Hydrocarbon Types Analysis of Gas-Oil Saturates Fractions by High Ionizing Voltage Mass Spectrometry Test Method for Estimating Apparent Vapor Pressures and Molecular Weights of Lubricating Oils Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography Test Method for Distillation of Crude Petroleum (15-Theoretical Plate Column) Test Method for Purity and Benzene Content of Cyclohexane by Gas Chromatography Test Method for Trace Quantities of Sulfur in Light Liquid Petroleum Hydrocarbons by Oxidative Microcoulometry Test Method for Viscosity of Asphalt with Cone and Plate Viscometer Test Method for Mercaptan Sulfur in Gasoline, Kerosine, Aviation Turbine, and Distillate Fuels (Potentiometric Method) Test Method for Salts in Crude Oil (Electrometric Method) Test Method for Solvent Extractables in Petroleum Waxes Test Method for Aromatic Types Analysis of Gas-Oil Aromatic Fractions by High Ionizing Voltage Mass Spectrometry Test Method for Thermal Oxidation Stability of Aviation Turbine Fuels (JFTOT Procedure) Test Method for Sulfur in Petroleum Gas by Oxidative Microcoulometry Test Method for Heptane Insolubles Test Method for Diesel Fuel Diluent in Used Diesel Engine Oils by Gas Chromatography Test Method for the Determination of Benzene and Toluene in Finished Motor and Aviation Gasoline by Gas Chromatography Practice for Containing Hydrocarbon Fluid Samples Using a Floating Piston Cylinder Test Method for Hydrogen Content of Aviation Turbine Fuels by Low Resolution Nuclear Magnetic Resonance Spectrometry

vii
287 302 307 311 318 322 327 334 337 342 346 352 355 358 361 365 368 373 379 385 392 402 406 413 420 426 432 439 444 455 484 488 494 498 503 508 514 527 538 545 548 552 559 563

viii

CONTENTS
Test Method for Boiling Range Distribution of Gasoline and Gasoline Fractions by Gas Chromatography Test Method for Analysis of Isopropyl Benzene (Cumene) by Gas Chromatography Test Method for Analysis of o-Xylene by Gas Chromatography Test Method for Analysis of p-Xylene by Gas Chromatography Test Method for Trace Quantities of Sulfur in Liquid Aromatic Hydrocarbons by Oxidative Microcoulometry Test Method for Water in Crude Oil by Distillation Test Method for Water and Sediment in Crude Oil by the Centrifuge Method (Laboratory Procedure) Test Method for Sulfur in Petroleum Products by Hydrogenolysis and Rateometric Colorimetry Test Method for Density and Relative Density of Liquids by Digital Density Meter Test Method for Benzene in Motor and Aviation Gasoline by Infrared Spectroscopy Practice for Manual Sampling of Petroleum and Petroleum Products Practice for Automatic Sampling of Petroleum and Petroleum Products Test Method for Trace Ethylene Glycol in Used Engine Oil Test Method for Sulfur in Petroleum Products by Energy-Dispersive X-Ray Fluorescence Spectroscopy Practice for Preparation of Liquid Blends for Use as Analytical Standards Test Method for Benzene in Hydrocarbon Solvents by Gas Chromatography Test Method for Water in Crude Oils by Potentiometric Karl Fischer Titration Test Method for Measurement of Transition Temperatures of Petroleum Waxes by Differential Scanning Calorimetry Test Method for Determination of Carbonyls in C4 Hydrocarbons Test Method for Butylene Analysis by Gas Chromatography Test Method for Analysis of Benzene by Gas Chromatography Test Method for Determination of Carbon Residue (Micro Method) Test Method for Benzene Content of Cyclic Products by Gas Chromatography Test Method for Analysis of Barium, Calcium, Magnesium and Zinc in Unused Lubricating Oils by Atomic Absorption Test Method for Trace Nitrogen in Liquid Petroleum Hydrocarbons by Syringe/Inlet Oxidative Combustion and Chemiluminescence Detection Test Method for Determination of Trace Thiophene in Refined Benzene by Gas Chromatography Test Method for Calculated Cetane Index by Four Variable Equation Test Method for Hydrogen Content of Light Distillates, Middle Distillates, Gas Oils, and Residua by Low Resolution Nuclear Magnetic Resonance Spectroscopy Test Method for Hydrogen Sulfide in Natural Gas Using Length-of-Stain Detector Tubes Test Method for Determination of MTBE, ETBE, TAME, DIPE, tertiary-Amyl Alcohol and Cl to C4 Alcohols in Gasoline by Gas Chromatography Test Method for Determination of Traces of Methanol in Propylene Concentrates by Gas Chromatography Test Method for Water Vapor in Natural Gas Using Length-of-Stain Detector Tubes Test Method for Elemental Analysis of Lubricant and Additive Components--Barium, Calcium, Phosphorus, Sulfur and Zinc by Wavelength-Dispersive X-Ray Fluorescence Spectroscopy Test Method for Water in Crude Oils by Coulometric Karl Fischer Titration Test Method for Determination of Organic Chloride Content in Crude Oil Test Method for Determination of Additive Elements in Lubricating Oils by Inductively Coupled Plasma Atomic Emission Spectrometry Test Method for Vapor Pressure of Gasoline and Gasoline-Oxygenate Blends (Dry Method) Test Method for Density and Relative Density of Crude Oils by Digital Density Analyzer Test Method for Determining Impurities in High-Purity Ethylbenzene by Gas Chromatography Test Method for Detailed Analysis of Petroleum Naphthas Through Nonane by Capillary Gas Chromatography Test Method for Analysis of Styrene by Capillary Gas Chromatography Test Method for Determination of Additive Elements, Wear Metals, and Contaminants in Used Lubricating Oils and Determination of Selected Elements in Base Oils by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) Test Method for the Determination of the Aromatic Content and Polynuclear Aromatic Content of Diesel Fuels and Aviation Turbine Fuels by Supercritical Fluid Chromatography Test Method for Vapor Pressure of Petroleum Products (Automatic Method) Test Method for Vapor Pressure of Petroleum Products (Mini Method) 567 578 582 586 590 596 606 617 621 625 628 646 670 673 676 679 684 688 691 694 696 700 705 708 712 716 720 723 728 731 739 744 747 753 760 766 771 778 783 786 797 800

D3710 D3760 D3797 D3798 D3961 D4006 D4007 D4045 D4052 D4053 D4057 D4177 D4291 D4294 D4307 D4367 D4377 D4419 D4423 D4424 D4492 D4530 D4534 D4628 D4629 D4735 D4737 D4808 D4810 D4815 D4864 D4888 D4927 D4928 D4929 D4951 D4953 D5002 D5060 D5134 D5135 D5185

D5186 D5190 D5191

806 811 816

CONTENTS D5194 D5234 D5236 D5273 D5274 D5287 D5291 D5292 D5303 D5307 D5384 D5386 D5442 D5443 D5453 D5454 D5482 D5503 D5504 D5580 D5599 D5622 D5623 D5708 D5713 D5762 D5769 D5776 D5799 D5808 D5842 D5845 D5853 D5863 D5917 D5986 D6069 D6144 D6159 Test Method for Trace Chloride in Liquid Aromatic Hydrocarbons Guide for Analysis of Ethylene Product Test Method for Distillation of Heavy Hydrocarbon Mixtures (Vacuum Potstill Method) Guide for Analysis of Propylene Concentrates Guide for Analysis of 1,3-Butadiene Product Practice for Automatic Sampling of Gaseous Fuels Test Method for Instrumental Determination of Carbon, Hydrogen, and Nitrogen in Petroleum Products and Lubricants Test Method for Aromatic Carbon Content of Hydrocarbon Oils by High Resolution Nuclear Magnetic Resonance Spectroscopy Test Method for Trace Carbonyl Sulfide in Propylene by Gas Chromatography Test Method for Determination of the Boiling Range Distribution of Crude Petroleum by Gas Chromatography Test Method for Chlorine in Used Petroleum Products (Field Test Kit Method) Test Method for Color of Liquids Using Tristimulus Colorimetry , Test Method for Analysis of Petroleum Waxes by Gas Chromatdgraphy Test Method for Paraffin, Naphthene and Aromatic Hydrocarbon Type Analysis in Petroleum Distillates Through 200C by Multi-Dimensional Gas Chromatography Test Method for Determination of Total Sulfur in Light Hydrocarbons, Motor Fuels, and Oils by Ultraviolet Fluorescence Test Method for Water Vapor Content of Gaseous Fuels Using Electronic Moisture Analyzers Test Method for Vapor Pressure of Petroleum Products (Mini Method-Atmospheric) Practice for Natural Gas Sample-Handling and Conditioning Systems for Pipeline Instrumentation Test Method for Determination of Sulfur Compounds in Natural Gas and Gaseous Fuels by Gas Chromatography and Chemiluminescence Test Method for Determination of Benzene, Toluene, Ethylbenzene, p/m-Xylene, o-Xylene, C9 and Heavier Aromatics, and Total Aromatics in Finished Gasoline by Gas Chromatography Test Method for Determination of Oxygenates in Gasoline by Gas Chromatography and Oxygen Selective Flame Ionization Detection Test Method for the Determination of Total Oxygen in Gasoline and Methanol Fuels by Reductive Pyrolysis Test Method for Sulfur Compounds in Light Petroleum Liquids by Gas Chromatography and Sulfur Selective Detection Test Method for Determination of Nickel, Vanadium, and Iron in Crude Oils and Residual Fuels by Inductively Coupled Plasma (ICP) Atomic Emission Spectrometry Test Method for Analysis of High Purity Benzene for Cyclohexane Feedstock by Capillary Gas Chromatography Test Method for Nitrogen in Petroleum and Petroleum Products by Boat-Inlet Chemiluminescence Test Method for Determination of Benzene, Toluene and Total Aromatics in Finished Gasoline by Gas Chromatography/Mass Spectrometry Test Method for Bromine Index of Aromatic Hydrocarbons by Electrometric Titration Test Method for Determination of Peroxides in Butadiene Test Method for Determining Organic Chloride in Aromatic Hydrocarbons and Related Chemicals by Microcoulometry Practice for Sampling and Handling of Fuels for Volatility Measurement Test Method for the Determination of MTBE, ETBE, TAME, DIPE, Methanol, Ethanol and tertButanol in Gasoline by Infrared Spectroscopy Test Method for Pour Point of Ct:ude Oils Test Method for Determination of Nickel, Vanadium, Iron, and Sodium in Crude Oils and Residual Fuels by Flame Atomic Absorption Spectrometry Test Method for Trace Impurities in Monocyclic Aromatic Hydrocarbons by Gas Chromatography and External Calibration Test Method for the Determination of Oxygenates, Benzene, Toluene, Cs-C12 Aromatics and Total Aromatics in Finished Gasolines by Gas Chromatography/Fourier Transform Infrared Spectroscopy (GC/FTIR) Test Method for Trace Nitrogen in Aromatic Hydrocarbons by Oxidative Combustion and Reduced Pressure Chemiluminescence Detection Test Method for Analysis of AMS (ct-Methylstyrene) by Gas Chromatography Test Method for Determination of Hydrocarbon Impurities in Ethylene by Gas Chromatography

ix 821 824 826 842 845 847 852 857 864 870 877 88O 883 890 900 906 908 912 917 922 931 939 943 948 953 956 961 972 975 977 981 988 993 1000 1005 1011

1025 1030 1034

CONTENTS

D6160 D6212

Test Method for Determination of Polychlorinated Biphenyls (PCBs) in Waste Materials by Gas Chromatography Test Method for Total Sulfur in Aromatic Compounds by Hydrogenolysis and Rateometric Colorirnetry

1039 1054

Introductory Information

Introduction

THE PETROLEUMANALYSTis a problem solver and, as such, is constantly required to make method choices. In the past, two questions were most frequently associated with the method selection process. What properties can be determined to solve a particular production problem? What methods are appropriate to determine a specific property? Now the analyst is faced with additional complications. These include the need to produce results faster, in more detail, at lower concentration levels; to reduce costs (usually in the form of analyst labor); and to provide higher-quality results. In addition, federal and state regulations, particularly on spark-ignition engine fuels, influence method choice. Thus, method choice is now even more difficult. Fortunately, technology has advanced dramatically. Instrumental techniques have prospered and continue to improve rapidly. Gas chromatography, long a mainstay, is using faster, more efficient columns along with element-specific detectors. Furthermore, hyphenated techniques such as gas chromatography-mass spectrometry (GC/MS) and liquid chromatography-mass spectrometry (LC/MS) are providing separations that were once only a vision. Other spectrometric techniques--near infrared (NIR), Fourier transform infrared (FTIR), and nuclear magnetic resonance (NMR), to name a few, are being utilized on-line virtually unattended to provide real-time data. Nevertheless, the method of choice will still depend on the boiling range (or carbon number) of the sample to be analyzed, and, following this, the resources available to the analyst. Therefore, in this manual, the hydrocarbons, along with their associated methods, are discussed according to boiling range. The first five chapters of this manual are arranged beginning with "Analysis of C5 and Lighter Hydrocarbons," followed by "Analysis of Gasoline and Other Light Distillate Fuels," "Analysis of Kerosine, Diesel, and Aviation Turbine Fuel," "Analysis of Viscous Oils," and "Analysis of Waxes." Chapter 6, "Analysis of Crude Oils," deals with the total span of compounds, from gases to non-distillables. Chapter 7, "Analysis of Aromatics Hydrocarbons," is a special case that discusses a particular class of compounds that has increasingly gained importance in octane enhancing and, particularly, in petrochemicals.

Table 1 shows the carbon number range and boiling points (of normal paraffins) for some of the more common petroleum products of commerce. ASTM methods that may be applied to these boiling ranges are shown in Table 2. These tables are provided as an overview of the complex hydrocarbon analysis field; they do not show all of the methods that might be applicable. Details on many of these analytical methods, as well as techniques and procedures under development, are discussed in the appropriate chapters. Crude petroleum and fractions (or products) obtained from it contain a complex variety of compounds. It is interesting to note that as the number of carbon atoms increases, the possible complexity of petroleum mixtures also rapidly increases (see Table 3). Consequently, detailed analysis of the higher boiling fractions becomes increasingly difficult. Instrumental techniques have improved this situation, and the data being obtained provide extremely valuable input for the design, control, and evaluation of petroleum processes. Traditionally, however, these techniques were not available, It was necessary (and in many cases, satisfactory) to empirically determine specific physical properties that could be related to product quality and process control. Although the number of these tests is diminishing, many of them are still in common use. Some appear in this text because product specifications reference them and some referee methods still utilize the more basic testing procedures. Additionally, "classes" or types of hydrocarbons were and still are determined based on the capability to isolate them by separation techniques. The four types usually sought are paraffins, olefins, naphthenes, and aromatics. Paraffinic hydrocarbons include both normal and branched alkanes. Olefins refer to normal and branched alkenes that contain one or more double or triple carbon-carbon bonds. Naphthene (not to be confused with "naphthalene") is a term of the petroleum industry that refers to the saturated cyclic hydrocarbons or "cycloalkanes." Finally, aromatics include all hydrocarbons containing one or more rings of the benzenoid structure. These general hydrocarbon classifications are complicated by many combinations of the above types, for example, olefinic aromatics (styrene) or alkylbenzenes (cumene). Table 4 presents a summary of the hydrocarbon types usually found in specific petroleum fractions.

MANUAL ON HYDROCARBON ANALYSIS

A A

A~

I r

V V

~+~

~+

"7

el

wg~

INTRODUCTORY INFORMATION
Table 2--Summary of ASTM Test Methods Number of CarbonAtoms Boiling Rangeof Normal Paraffmsat 760 mm Hg, C
C1-C2 -161 to -89

C:Cs -42to +36

Co.-CIo 6 9 t o 174

CH-CI~ 196 to 270

C~s-Czo 287 to 343

>(2)) >355

Physical Methods D5, Penetration of bituminous materials D36, Ring and ball softening point D56, Flash by tag closed cup tester D86, Distillation of petroleum products D87, Melting point of wax
D92, Flash and fire Cleveland open cup D93, Flash and fire by Pensky-Martens closed cup D97, Pour point D 127, Melting point of wax D189, Couradson carbon residue D287, API gravity by hydrometer D323, Vapor pressure (Reid method) D445, Kinematic viscosity D447, Distillation of plant spray oils D473, Sediment by extraction 13482, Ash from petroleum products D524, Ramsbottom carbon residue D611, Aniline point D721, Oil content of petroleura waxes D850, Distillation of industrial aromatics D852, Solidification point of benzene D972, Evaporation losses of greases & oils DlOIS, Purity from freezing point DI016, Purity from freezing point D 1078, Distillation of volatile organic liquids

X X X X X X X X X
X

X X

X X

X X X X X X X X X X X X X X X X X X X X X X x X X X X X X X X X
I

X X X

X X X X

X X

X X

D1142, D 1160, D 1218, D1267, D 1298,

Water vapor of gaseous fuels Distillation at reduced pressure Refractive index & dispersion Vapor pressure of LP gases Relative density of liquids

X X X X X

D 1322, Smoke point of aviation turbine fuels D 1493, Solidification point of organic chemicals D 1657, Relative density of light hydrocarbons D 1747, Refractive index of viscous materials D 1807, Refractive index of insulating oils D1837, Volatility of LP gases D2158; Residue in LP gases D2171, Viscosity of asphalts D2386, Freezing point of aviation fuels D2500, Cloud point of peltoleum oils

X X

X X
X X X X X

MANUAL ON HYDROCARBON ANALYSIS T a b l e 2 - continued


Number of Carbon Atoms Boiling Range of Normal Paraffins at 760 nun Hg, C
CI-C2 -161 to -89

C3-C~ -42to +36

C6-C1o
6 9 t o 174

Cu-C~5 196 to 270

Ct,-C2o 287 to 343

>C~ >355

D2503, Molecular weight D2533, Vapor-liquid ratio of gasoline D2892, Distillation of crude oil D3205, Viscosity of asphalt (cone & plate) D3279, n-Heptane insolubles D3828, Flash point by Seta flash closed tester D4052, Density by digital density meter D4206, Sustained burning test by Seta flash D4207, Sustained burning test by wick method D4530, Micro carbon residue D4809, Precise heat of combustion D4953, Vapor pressure of gasoline oxygenate blends D5002, Density of erude oil D5 ! 90, Vapor pressure (automatic method) D5 ! 91, Vapor pressure (mini method) D5236, Distillation of heavy oils D5482, Vapor pressure of petroleum products D5853, Pour point of crude oils Correlative Methods D341, Viscosity-temperature charts for hydrocarbons D976, Calculation of octane index of distillate fuels D 1250, Petroleum measurement tables D2270, Calculation of viscosity index D250 !, Viscosity-gravityconstant of oils D2502, Molecular weight of oils D2598, Physical properties of LP gases D2889, Calculation of true vapor pressure D3238, Carbon distribution & structure analysis, n-d-M D3338, Estimation of heat of combustion of aviation fuels D3343, Hydrogen content of aviation gasoline D4529, Estimation of heat of combustion of aviation fuels D4737, Calculated oetane index Liquid Chromatographic Methods D 1319, Hydrocarbon types by FIA D2007, Rubber extender & processing oils D2549, Aromatics & nonaromatics in distillates D5186, Aromatics in diesel fuel by SFC Gas Chromatographic Methods D1945, Analysis of natural gas D1946, Analysis of reformed gas D2163, LP gases & propylene concentrates D2268, High-purity heptane & isooctane D2306, Xylene isomers in xylene X X X X X X X

X X X X X X X X X X X X X X X X X X X X X X X X

X X X X X X X

X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X

X X

X X X X

X X

X X

INTRODUCTORY INFORMATION
Table 2 - continued
Number of Cazbon Atoms CcC~ C~'Cs C.-Cis 196 to 270 C,6-C~ 287 to 343 >C= >355

Cs-Clo

BoilingRange of NormalPaxaffmsat 760 mm Hg, C


....,

-161to -89

-42to +36 X X X X X X X X

69to 174

D2360, D2426, D2427, D2504, D2505,


,, ,

Trace impurities in aromatics Butadiene dimer & styrene C2-C5 in gasoline Nonenndensibles in C3 & lighter Analysis of high-purity ethylene Butadiene purity and hydrocarbon impurities Natural gas-liquid mixtures Hydrocarbon Iraces in propylene C,-C~ hydrocarbons in atomosphere Boiling range distribution of petroleum fractions Cyolohexane purity & benzene content Diesel fuel in used iubc oils Gasoline diluent m engine oils Benzene & toluene in gasoline Boiling range distribution of gasoline Analysis of isopropylbenzene Purity of o-xylene Purity of p-xylene Analysis of styrene Benzene content of solvents Aromatics in finished gasolines Butane-butene mixtures Purity of benzene Benzene content of cyclic hydrocarbons Calculation of response factors Trace thiophene in benzene Alcohols and MTBE in gasoline Methanol in propylene Impurities in ethylbenzene Analysis of naphthas Analysis of styrene Trace COS in propylene Boiling range distribution of crude oil Petroleum wax Hydrocarbon types Sulfur compounds by GC & chemiluminescence

X X X X X X X X

D2593, D2597, D2712, D2820, D2887, D3054, D3524, D3525, D3606, D3710, D3760. D3797, D3798. D3962, D4367, D4420, D4424, D4492, D4534, D4626, D4735. IM815, D4864, D5060, D5134, D5135, D5303, D5307, D5442, D5443, D5504,

X X

X X X X

X X

X X

X X X X X X X X X

X X X X X X X X X X X X X X X X X X X X X X X X X X X

D5580, Aromatics in gasoline D5599,'Oxygenates in gasoline by GC & OFID D5623, Sulfur compounds by GC & sulfur selective detector D5713, Benzene purity D5769, Aromatics in gasoline by GC-MS

MANUAL ON HYDROCARBON A N A LYSI S


T a b l e 2 - continued
Number o f Carbon Atoms Boiling Range o f Normal Paraffins at 760 m m Hg, C C~-C2 -161 to -89 C:Cs -42 to +36

C6-Cio
69to 174

Cu-Cls 196to 270

C,6-C20 287to 343

>Cm >355

D5917, Trace impurities in aromatics D5986, Oxygenates and aromatics in gasoline by GC/FTIR I)6144, Analysis of cx-methylstyrene 136159, Impurities in ethylene D6160, PCBs in waste material Spectroscopic Methods D 1840, Naphthalenes in aviation turbine fuels D2425, Hydrocarbon types in distillates by MS D2650, Chemical composition of gases by MS D2786, Analysis of gas-oil saturate fractions by MS D2789, Hydrocarbon types in gasoline by MS D3239, Aromatic types in gas oil aromatic fractions by MS D3701, Hydrogen content of fuels by NMR D4053, Benzene content of gasoline by IR D4808, Hydrogen content of petroleum products by NMR D5292, Aromatic carbon and hydrogen by NMR D5845, Oxygenates in gasoline by IR Chemical Methods D483, Unsulfonated residue of spray oils I)664, Neutralization number by potentiometric titration D847, Acidity in solvent naphthas and aromatics D974, Neutralization number by color-indicator method D 1159, Bromine number by electrome~c titration
D 1492, Bromine index of aromatics D2710, Bromine index by electrometric titration D4423, Carbonyl in C4 hydrocarbons D5776, Bromine index D5799, Peroxides in butadiene Miscellaneous Methods

X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X

X X X X

X X X X X X X

D 130, Copper strip corrosion D156, Saybolt color D ! 87. Burning quality of kerosine D381, Existent gum in fuels D525, Oxidation stability of gasoline (induction period) D613, Cetane quality of diesel fuels D848, Acid wash color of aromatics D849, Copper corrosion of aromatics D873, Oxidation stability of aviation fuels D909, Knock characteristics of aviation fuels D 1133, Kauri-Butanol value D1265, Sampling LP gas D2121, Polymer in styrene D2274, Oxidation stability of distillate fuels D2276, Particulate contamination in aviation turbine fuels X

X X X X X X X

X X X X

X X X X X X X X X

INTRODUCTORY INFORMATION

T a b l e 2 - continued
Number of Carbon Atoms Boiling Range of Normal P~affms at 760 mm Hg, C CcC~ -161 to -89 C3-Cs -42 to +36

Ce,-CIo
69to 174

Cn-Cts 196 to 270

C~6-C~o 287 to 343

>(22o >355

D2624, Electrical conductivity of aviation and distillate fuels D2699, Knock characteristics by research octane D2700, Knock characteristics by motor octane D2713, Dryness of propane (valve freeze) D2780, Solubility of fixed gases in liquids

X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X

D2878, D2885, D3235, D3241, D3700,

Estimating vapor pressure of lubricating oils Knock characteristics by on-line analyzers Solvent extractables in waxes Thermal oxid. stab. of aviation turbine fuel (JFTOT) Sampling using floating piston cylinder

X X X X X X X X X X

X X

D3948, Water separation charact, of aviation turbine fuel D4057, Manual sampling of petroleum D4 i 77, Automatic sampling of petroleum D4291, Ethylene glycol in used engine oil D4307, Preparation of liquid blends D4419, Transition temperatures of wax by DSC D4740, Stability of residual oils by spot test D5184, AI and Si in fuel oils by ICP-AES and AAS D5234, Guide for analysis of ethylene D5273, Guide for analysis of propylene D5274, Guide for analysis of butadiene D5287, Automatic sampling of gaseous fuels D5386, Color of liquids D5503, Natural gas sample-handling D5842, Sampling of fuels for volatility

X X

Non-Hydrocarbon Methods D95, Water by distillation D96, Water and sediment in crude oils D129, Sulfur by bomb method D808, Chlorine in petroleum products D853, H2S and SO2in aromatics
D!266, Sulfur by lamp method D1552, Sulfur by high-temperature method D1685, Thiophene in benzene D1988, Mercaptans in natural gas D2420, Hydrogen sulfide in LP gases D2622, Sulfur by X-ray D2709, Water and sediment in fuels D2784, Sulfur in LP gases D3120, Trace sulfur by oxidative microcoulometry D3227, Mercaptans in distillates (potentiometric)

X X X X X

X X X X

X X X X

X X X X X X X X X X X X X X X X X

X X

X X

10

MANUAL ON HYDROCARBON A N A L Y S I S
Table 2 - continued

Number of Carbon Atoms Boiling Range of Normal Paraffins at 760 mm Hg, C D3230. D3231, D3237, D3246, D3341, Salt in crude oil Phosphorus in gasoline Lead in gasoline by AAS Sulfur in gases by oxidative microcoulometry Lead in gasoline (iodine monochloride)

CfC~ -161 to -S9

C.-Cs -42 to +36 X

c.-c,o
69to 174

Cn'C~5 196 to 270

C~6-C2o 287 to 343

>C~ >355

X X X X

X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X

D3605, Trace metals in fuels by AAS D3961, Sulfur in aromatics by oxidative microcoulometry D4006, Water in crude oil by distillation D4007, Water and sediment in crude oil by centrifuge D4045, Sulfur by hydrogenolysis and rateometric colorimetry IM047, Phosphorus in lubricating oils D4294, Total sulfur by XRF D4377, Water in crude oil by Karl Fischer D4628, Ba, Ca, Mg, and Zn in oils by AAS D4629, Trace nitrogen by chemiluminescence

1)4810, H2Sin natural gas


D4888, Water in natural gas D4927, Ba, Ca, P, S and Zn by XRF D4928, Water in crude oils IM929, Chloride in crude oils
134951, D5185, D5194, D5291, D5384, D5453, D5454, D5622, D5708, D5762, Additive elements in lube oils by ICP-AES Additive elements in lube oils by ICP-AES Trace chloride in aromatics C, H and N in petroleum products Chlorine in used oils Sulfur in fuels and oils Water vapor in gaseous fuels Total oxygen by reductive pyrolysis Ni, V and Fe in crude oil by ICP-AES Nflrogen by chemiluminescence Organic chloride in aromatics by microenulometry Ni, V, Fe and Na in crude oil by AAS Trace nitrogen in aromatics by chemiluminescence Total sulfur in aromatics by rateometric colorimetry

X X

X X X X X X X X X X X X X X X X X X X X X X X X X X

X X X X X X X X X X X X X X X X

D5808, D5863, D6069, D6212,

INTRODUCTORY

INFORMATION

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12

MANUAL ON HYDROCARBON A N A L Y S I S
chromatography (ASTM Test Methods D2887 on Boiling Range Distribution of Petroleum Fractions by Gas Chromatography and D3710 on Boiling Range Distribution of Gasoline and Gasoline Fractions by Gas Chromatography) as compared to physical distillation (ASTM Test Methods D86 on Distillation of Petroleum Products at Atmospheric Pressure and D 1160 on Distillation of Petroleum Products at Reduced Pressures). ASTM Subcommittee D02.04 on Hydrocarbon Analysis is actively engaged in finalizing this particular correlation. Other correlation methods are available, some of which are listed in Table 2. As analytical technology and the petroleum industry change, older methods will be revised or discontinued and new ones developed. Within this dynamic system, new challenges will continue to face the analyst as quickly as older problems are solved. Through the efforts of ASTM members, new concepts will be evaluated, proven, and formalized as consensus test methods. A. W. Drews Subcommittee D02.04 on Hydrocarbon Analysis

A manual on hydrocarbon analysis would not be complete without considerable attention to non-hydrocarbons that occur in all crude oils and products. These impurities can range in concentration from parts-per-billion to percent levels, depending on the type of crude oil or specific fraction. Accurate determination of elements such as sulfur, nitrogen, or oxygen as well as numerous metals can be of the utmost importance. The analyst is constantly being challenged to determine these materials at lower and lower levels. Even minute concentrations of these elements can be fatal to sensitive catalytic systems that are now being used in most refining processes. With the introduction of oxygenated motor fuels, the determination of oxygen-containing compounds has become mandatory while complicating the determination of hydrocarbons in their presence. Finally, a word on correlative methods. Numerous calculation methods have been developed to relate chemical or physical properties to composition or processability. Other correlative methods allow direct comparison of data that have been obtained by totally different procedures. A particularly good example of this is the correlation of boiling range by gas

Part l--Discussion of Analyses

by Product Type

Analysis of Cs and Lighter Hydrocarbons


by Neil G. Johansen
INTRODUCTION
THE LIGHTHYDROCARBONS--methane (C~), ethane (C2), propane (Ca), and the butanes (C4), either in the gas phase or liquefied, are primarily used for heating, motor fuels, and as feedstocks for chemical processing. The pentanes/pentenes (C5) are products of natural gas or petroleum fractionation or refinery operations (i.e., reforming and cracking) that are removed for use as chemical feedstocks. The olefins--ethene (ethylene), propene (propylene), butenes (butene-1, isobutylene, cis- and trans-butene-2, and the butadienes), pentenes, and pentadienes are materials produced by various refining processes involving the use of the saturated hydrocarbons as feedstocks. Mixtures of these hydrocarbons are commonly encountered in material testing, and the composition varies depending upon the source and intended use of the material. Other non-hydrocarbon constituents of these mixtures are important analytes since they may be useful products or may be undesirable as a source of processing problems. Some of these components are helium, hydrogen, argon, oxygen, nitrogen, carbon monoxide, carbon dioxide, sulfur, and nitrogen containing compounds, as well as heavier hydrocarbons. Desired testing of these hydrocarbon mixtures usually involves the determination of bulk physical or chemical properties and component speciation and quantitation. ASTM addresses the characterization and specification of the C~ to C5 hydrocarbon materials and products through several venues. Committee D03 is responsible for gaseous fuels; Committee D02, Subcommittee H is responsible for liquefied petroleum gas; Committee D02, Subcommittee D is responsible for hydrocarbons for chemical and special uses, while Committee D02, Subcommittee 4 has responsibility for test methods involving hydrocarbons in general. Committees D19 (Water) and D22 (Sampling and Analysis of Atmospheres) address environmental concerns involving light hydrocarbons.

ble among these are ASTM Standard Practices D5287, Automatic Sampling of Gaseous Fuels,1 D5503, Natural Gas Sample-Handling and Conditioning Systems for Pipeline Instrumentation, I D1265, Sampling Liquefied Petroleum (LP) Gases (Manual Method), l and D3700, Containing Hydrocarbon Fluid Samples Using a Floating Piston Cylinder? Sampling of low-pressure materials is described in ASTM Standard Practices D4057, Manual Sampling of Petroleum and Petroleum Products/ D4177, Automatic Sampling of Petroleum and Petroleum Products, ~ and D5842, Sampling and Handling of Fuels for Volatility Measurement. 1 The preparation of gaseous and liquid blends is described in ASTM Standard Practices D4051, Preparation of LowPressure Gas Blends, 2 and D4307, Preparation of Liquid Blends for Use as Analytical Standards. 1 While sampling of C1 and C2 hydrocarbons is typically performed using stainless steel cylinders, either lined or unlined, other containers are employed dependent upon particular situations; for example, glass cylinder containers or PVF sampling bags. The preferred method for sampling Ca and C4 hydrocarbons is by the use of piston cylinders, ASTM Standard Practice D3700, although sampling these materials as gases is also acceptable in many cases. The sampling of C5 and higher hydrocarbons is dependent upon the vapor pressure of the sample. Piston cylinders or pressurized steel cylinders are advisable for high-vapor pressure samples (containing significant amounts of light gases), while atmospheric sampling may be used for low-vapor pressure samples.

Analysis
ASTM test methods for gaseous fuels and petroleum products have been developed over many years, extending back into the 1930s. Bulk physical property tests, such as density and heating value, as well as some compositional tests, such as the Orsat analysis and the mercuric nitrate method for the determination of unsaturation, were widely used. Mass spectrometry became the method of choice for compositional analysis of light hydrocarbons, and ASTM Test Method D2650, Chemical Composition of Gases by Mass Spectrometry/ was standardized in 1967 to replace several older methods. Currently the mass spectrometry method has been replaced, in practice, by gas chromatography as the technique of choice for fixed gas and hydrocarbon speciation. 1Appears in this publication.
2Annual Book of ASTM Standards, Vol. 05.02.

CURRENT PRACTICES

Sampling
One of the more critical aspects for the analysis of light hydrocarbons is the question of sampling. Sampling of gaseous and liquefied materials is addressed in a variety of specific sampling methods, and many of the test methods themselves contain additional sampling requirements. Nota-

15

16

MANUAL ON HYDROCARBON ANALYSIS

Natural and Reformed Gas


ASTM Test Method D1945, Analysis of Natural Gas by Gas Chromatography, ~and ASTM Practice D 1946, Analysis of Reformed Gas by Gas Chromatography, 1 describe procedures for the determination of hydrogen, helium, oxygen, nitrogen, carbon monoxide, carbon dioxide, methane, ethene, ethane, propane, butanes, pentanes, and hexanes-plus in natural and reformed gases by packed column gas chromatography. These compositional analyses are used to calculate many other properties of gases, such as density, heating value, and compressibility. The first five components listed are determined using a molecular sieve 13X column (argon carrier gas), while the remaining components are determined using polydimethylsiloxane partition or porous polymer columns. The hexanes-plus analysis is accomplished by backflushing the column after the elution of pentane or by the use of a bacldlushed precolumn. Important constituents of natural gas not accounted for in these analyses are moisture (water) and hydrogen sulfide, as well as other sulfur compounds. Water content is determined by ASTM Test Methods D 1142, Water Vapor Content of Gaseous Fuels by Measurement of Dew-Point Temperature, ~ D5454, Water Vapor Content of Gaseous Fuels Using Electronic Moisture Analyzers, ~ or D4888, Water Vapor in Natural Gas Using Length-of-Stain Detector Tubes) ASTM Test Method D5504, Sulfur Compounds in Natural Gas and Gaseous Fuels by Gas Chromatography and Chemiluminescence, I best accomplishes sulfur compound determination, although ASTM Test Methods D 1988, Mercaptans in Natural Gas Using Length-of-Stain Detector Tubes, ~ and D4810, Hydrogen Sulfide in Natural Gas Using Length-ofStain Detector Tubes, ~ can also be used with some loss in accuracy.

Light Olefins (C2, C3, C. and C5)


Characteristics and corresponding test methods for these materials have been outlined in three ASTM standard guides: D5234, Analysis of Ethylene Product, ~ D5273, Analysis of Propylene Concentrates, 1 and D5274, Analysis of 1,3Butadiene Product. 1 A proposed Guide for the Analysis of Isoprene is being developed. These guides list properties to be measured and the range of values expected, as well as appropriate test methods where available. Hydrocarbon analysis of ethene is accomplished using ASTM Test Methods D2505, Ethylene, Other Hydrocarbons, and Carbon Dioxide in High-Purity Ethylene by Gas Chromatography, l and ASTM Test Method D6159, Hydrocarbon Impurities in Ethylene by Gas Chromatography.l D6159 is a new test method using wide-bore (0.53-mm) capillary columns, including a A1203/KCI PLOT column. Currently, ASTM Test Method D2504 is recommended for determination of noncondensable gases, and ASTM Test Method D2505 is used for the determination of carbon dioxide; however, a new method is under development in ASTM to address these analyses. ASTM Test Methods D2712, Hydrocarbon Traces in Propylene Concentrates by Gas Chromatography, 1 and D2163, also a gas chromatographic method, are currently recommended for the determination of hydrocarbon impurities in propene. ASTM Test Method D4864, Determination of Traces of Methanol in Propylene Concentrates by Gas Chromatography, l is used for methanol determination. ASTM Test Method D5303, Trace Carbonyl Sulfide in Propylene by Gas Chromatography, 1 is used for carbonyl sulfide determination with a flame photometric detector. ASTM Test Method D3246, Sulfur in Petroleum Gas by Oxidative Microcoulometry, 1 is currently recommended for the determination of total sulfur, and the method is being revised to be more generally applicable to light hydrocarbon analysis. Commercial butylenes, high-purity butylenes, and butanebutylene mixtures are analyzed for hydrocarbon constituents by ASTM Test Method D4424, Butylene Analysis by Gas Chromatography) Hydrocarbon impurities in 1,3-butadiene are determined by ASTM Test Method D2593, Butadiene Purity and Hydrocarbon Impurities by Gas Chromatography) Butadiene dimer and styrene are determined in butadiene using ASTM Test Method D2426, Butadiene Dimer and Styrene in Butadiene Concentrates by Gas Chromatography) Carbonyls in C4 hydrocarbons are determined by a titrimetric technique using ASTM Test Method D4423, Determination of Carbonyls in C4 Hydrocarbons. ~ ASTM Test Method D5799, Determination of Peroxides in Butadiene, t is used for peroxide determination.

Liquefied Petroleum (LP) Gases


Propane, iso-butane, and butane generally constitute this sample type and are used for heating, motor fuels, and as chemical feedstocks. ASTM Test Methods D2597, Analysis of Demethanized Hydrocarbon Liquid Mixtures Containing Nitrogen and Carbon Dioxide by Gas Chromatography,l D2163, Analysis of Liquefied Petroleum (LP) Gases and Propene Concentrates by Gas Chromatography, l and D2504, Noncondensable Gases in C2 and Lighter Hydrocarbon Products by Gas Chromatography, ~ are methods for determining light hydrocarbons and some fixed gases in LP gases. Total sulfur is determined by ASTM Test Method D2784, Sulfur in Liquefied Petroleum Gases (Oxy-Hydrogen Burner or Lamp). ) Sulfur compound determination is made using ASTM Test Method D5623, Sulfur Compounds in Light Petroleum Liquids by Gas Chromatography and Sulfur Selective Detection. ~Trace total organic and bound nitrogen is determined using ASTM Test Method D4629, Trace Nitrogen in Liquid Petroleum Hydrocarbons by Syringe/Inlet Oxidative Combustion and Chemiluminescence Detection.~ The current test method for heavy residues in LP gases is ASTM Test Method D2158, Residues in Liquefied Petroleum (LP) Gases, t which involves evaporation of an LP Gas sample, measuring the volume of residue and observing the residue for oil stain on a piece of filter paper.

FUTURE TRENDS
In general, gas chromatography will undoubtedly continue to be the method of choice for characterization of light hydrocarbon materials. New developments in higher-speed techniques for gas chromatographic instrumentation and data processing will lead to new and revised test methods. New and improved detection devices and techniques, such as chemiluminescence, atomic emission, and mass spectroscopy, will enhance selectivity, detection limits, and analytical productivity. Laboratory automation through autosampling,

CHAPTER 1--ANALYSIS OF Cs AND LIGHTER HYDROCARBONS


computer control, and data handling will provide improved precision and productivity, as well as simplified method operation. Development of test methods for process (on-line) analysis and validation of these analyses are continuing under the direction of ASTM Committee D02.0D, Section l and D02.25. A proposed gas chromatographic/selective detection method is under development for the trace analysis of sulfur compounds in ethene and propene. ASTM Test Method D2163 is quite old. It utilizes lower resolution packed columns, a less sensitive detector, and manual peak area measurement. Thus, it is technically out of date, and Committee D02.0D is currently in the process of developing a revision for the determination of hydrocarbons in LP gases and lower-purity mixtures of C3 and C4 hydrocarbons. The revision will still be performance based, but the recommended column will be the A1203/KC1 PLOT column, as used in the recently standardized ASTM Test Method D6159,

17

as well as in another test method under development for high-purity propene. A continuing problem for LP gas characterization is the accurate determination of heavy residues (i.e., oils) in LP gas. New test methods have been proposed using procedures similar to those employed in gas chromatographic simulated distillation, and this development work is continuing. The development of test methods for C5 hydrocarbons (olefins) has begun recently and should result in ASTM standards in the near future. Various petroleum refinery process streams, often containing olefinic compounds, are generically referred to as "refinery gas." Although no ASTM test method is available for this determination, several instrumentation and technology suppliers market automated gas chromatographic systems as "refinery gas analyzers." ASTM standardization of this technology would be beneficial to users of these analyzers.

Analysis of Gasoline and Other Light Distillate Fuels


by James M. McCann
INTRODUCTION
THE CHALLENGETO DEVELOPmore accurate and precise test methods for the analysis of gasoline or automotive sparkignition engine fuel has been tremendously influenced by federal and state regulations covering the production of reformulated gasolines (RFG) with tight limits on many parameters [1]. 1 Examples of these new fuels include U.S. Environmental Protection Agency (EPA) RFG and California Air Resources Board (CARB) Phase 2 Gasoline. The regulated RFG test parameters include vapor pressure, distillation, benzene content, total aromatics, total olefins, individual oxygenates, oxygen content, and total sulfur. Regulatory requirements have enhanced the need for better test methods to control manufacturing and the distribution of gasolines. The addition of alcohol and ether as important blending components to gasoline to meet air quality standards has necessitated modifying some existing test methods and the development of new procedures. The desire to reduce manufacturing costs, coupled with the regulatory requirements, have enhanced the application of more cost effective test methods including rapid screening procedures and wider use of online analyzers. In this chapter, a brief history of ASTM method development for hydrocarbon analysis of gasoline is given. The focus, however, will be on some of the test parameters required for today's reformulated gasolines including many of the new test methodologies. ASTM standardization of methods for hydrocarbon analysis started in 1942 when Committee D02, Technical Division on Gasoline, established a subgroup to standardize a procedure for the determination of aromatics in gasolines for use by the military. This method was first issued in March of 1943 as Emergency Standard ES 45, Test for Olefins, Aromatics, Paraffins, and Naphthenes in Aviation Gasoline (Without Distillation Into Fractions). 2 This method was a combination of several procedures, some of which are still commonly used. In 1948, a procedure was described by A. L. Conrad and later refined by D. W. Cridle and R. L. LeTourneau for determining olefins, aromatics, and saturates in cracked gasoline. This procedure evolved into ASTM Test Method D1319, Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption, 3 often abbreviated as "FIA."

During the early 1950s, instrumental analytical techniques, such as mass spectrometry, infrared, and ultraviolet spectroscopy, were being explored and used for hydrocarbon composition and structural analysis. Beginning with the mid 1950s, publications on gas chromatography began to appear in the literature, and this new technique was soon being used for analyzing a wide variety of hydrocarbon streams. As commercial instrumentation was developed, the application of gas chromatography grew rapidly, with volumes of information being published from its beginning up to the present time. Recently, more rapid spectrometry methods such as infrared and near-infrared and the use of hyphenated analytical techniques, for example GC-MS, have been applied.

CURRENT PRACTICES Analysis of Gasoline Range Hydrocarbons


The following is a review of applicable test methods that can be used to measure some of the key parameters in gasoline range hydrocarbons.

Distillation
The primary method specified for determining boiling range of gasoline continues to be ASTM Test Method D86, Distillation of Petroleum Products at Atmospheric Pressure. 3 The use of automated instrumentation has been incorporated into the method. ASTM Test Method D3710, Boiling Range Distribution of Gasoline and Gasoline Fractions by Gas Chromatography, 3 (GC), can be used for determining the boiling point properties of oxygenate-free gasoline distillates. ASTM D3710 has the advantage that it uses a smaller sample size and can be more easily automated, but D3710 data are not directly equivalent to that obtained by D86 distillation. ASTM D3710 data are being used by some companies and vendors by applying correlations to predict D86 distillation data for various refinery streams. Improvements in the GC simulated distillation procedures have been implemented in some laboratories and are being evaluated in ASTM D02.04, Section H. Improvements include rapid gas chromatography techniques using very narrow bore capillary gas chromatography columns that will potentially reduce analysis time to a few minutes [2].

~The italic numbers in brackets refer to the references at the end of this chapter. 21944 Annual Book of ASTM Standards, Part III. 3Appears in this publication.

Vapor Pressure
The vapor pressure of gasoline is a critical physical test parameter for today's gasoline. ASTM Test Method D323,

18

CHAPTER 2--ANALYSIS OF GASOLINE AND OTHER DISTILLATE FUELS


Vapor Pressure of Petroleum Products (Reid Method), 3 had been widely used in the past. ASTM Test Method D5191, Vapor Pressure of Petroleum Products (Mini Method), 3 is now most commonly referenced in gasoline regulations. This method requires less sample and is much easier and faster to run. Other ASTM Test Methods for vapor pressure of gasoline include D4953, Vapor Pressure of Gasoline and Gasoline-Oxygenate Blends (Dry Method), a D5190, Vapor Pressure of Petroleum Products (Automatic Method), 3 and D5482, Vapor Pressure of Petroleum Products (Mini MethodAtmospheric). 3

19

Oxygenates
ASTM test methods have been developed to measure ethers and alcohols in gasoline range hydrocarbons, because oxygenated components such as methyl-tert-butylether and ethanol are common blending components in current gasolines. ASTM Test Methods D4815, MTBE, ETBE, TAME, DIPE, tertiary-Amyl Alcohol and C1 to C4 Alcohols in Gasoline by Gas Chromatography, a and D5599, Oxygenates in Gasoline by Gas Chromatography and Oxygen Selective Flame Ionization Detection, 3 were adopted for measuring oxygenates and oxygen content. ASTM D4815 is a widely used method and is currently the designated test method in California. ASTM D5599 is a GC capillary column method employing an oxygen selective flame ionization detector and was based upon the EPA designated test for oxygenates in gasoline [3 ]. It can detect any oxygenated component that elutes from the gas chromatographic (GC) column. ASTM D5986, Oxygenates, Benzene, Toluene, C8-C12 Aromatics and Total Aromatics in Finished Gasoline by Gas Chromatography/Fourier Transform Infrared Spectroscopy (GC/FTIR), 3 is more complex, but it can determine oxygenates, benzene, and total aromatics in a single analysis. ASTM Test Method D5622, Total Oxygen in Gasoline and Methanol Fuels by Reductive Pyrolysis, 3 can be used to directly determine mass percent total oxygen in fuels. ASTM Test Method D5845, MTBE, ETBE, TAME, DIPE, Methanol, Ethanol and tert-Butanol in Gasoline by Infrared Spectroscopy,3 is particularly useful as a rapid portable screening tool for oxygenates in gasoline. In addition, gas chromatography with an atomic emission detector has been used by laboratories to measure specific oxygenated components in gasoline [4,5 ].

was developed to include fuels containing commonly encountered alcohols and ethers. D5580 has been accepted as the designated test for determining benzene and total aromatics in California Phase 2 gasolines. Hyphenated analytical instrumental methods including ASTM Test Method D5769, Benzene, Toluene and Total Aromatics in Finished Gasolines by Gas Chromatography/Mass Spectrometry3 (GC/MS), and ASTM D5986, (GC/FTIR), also accurately measure benzene in gasoline. ASTM D5769 is based upon the EPA GC/MS procedure for aromatics [6 ]. The results of ASTM D02 Subcommittee 4 round robin studies have shown that there is no significant bias among methods D5769, D5580, and D5986 for benzene in gasoline. Benzene can also be measured by ASTM Test Method D4053, Benzene in Motor and Aviation Gasoline by Infrared Spectroscopy? Other improved infrared procedures are being considered for standardization in ASTM. ASTM D 1319 (FIA) has traditionally been used to measure aromatics as well as olefins and saturates in gasoline. ASTM Test Method D5443, Paraffin, Naphthene, and Aromatic Hydrocarbon Type Analysis in Petroleum Distillates through 200C by Multi-Dimensional Gas Chromatography, 3 can be used to measure hydrocarbon types by carbon number. Olefins, if present, are converted to saturates and are included in the paraffin and naphthene distribution. The scope of ASTM D5443 excludes hydrocarbons containing oxygenates. An extended version of the technique, which has not been standardized, measures paraffins, isoparaffins, olefins, naphthenes, and aromatics (PIONA) in gasoline range hydrocarbons [6 ]. ASTM Test Methods D5580 (GC), D5769 (GC/ MS), and D5986 (GC/FTIR) were adopted as a new test methods for aromatics in gasoline including fuels containing oxygenates. ASTM D5769 is based upon an EPA procedure for aromatics in gasoline [7 ]. The results of these total aromatics tests are not necessarily equivalent.

Total Olefins
ASTM Test Method D 1319 (FIA) is widely used for measuring total olefins in gasoline fractions as well as aromatics and saturates. D 1319 results must be corrected for the presence of oxygenates, and the precision of the method is poor. A titration procedure, ASTM Test Method D 1159, Bromine Number of Petroleum Distillates and Commercial Aliphatic Olefins by Electrometric Titration, 3 provides an approximation of olefin content within a sample, while ASTM Test Method D2710, Bromine Index of Petroleum Hydrocarbons by Electrometric Titration, 3 can be valuable for determining trace olefin levels. These methods do not directly measure total olefins, and the results are affected by the type of olefinic compound present. Cooperative studies are underway in ASTM D02.04 to find a better test method for total olefins. Cooperative work has been done to validate new gas chromatographic methods that trap the olefins on silver nitrate impregnated traps. These include a gas chromatographic multi-dimensional procedure for oxygenates and paraffin, olefin, naphthene, aromatic (O-PONA) hydrocarbon types in petroleum distillates and a GC fast total olefins analyzer (FTO) method. The FTO method has the advantage that the analysis time is quicker. The O-PONA method is an expanded version of ASTM D5443 and

Benzene and Aromatics


The accurate measurements of benzene and total aromatics in gasoline are regulated test parameters in modern gasoline. ASTM Test Method D3606, Benzene and Toluene in Finished Motor and Aviation Gasoline by Gas Chromatography, 3 (GC), is a procedure accepted by the EPA as the designated test for benzene in gasoline. The precision and accuracy of D3606 is diminished in gasolines containing ethanol or methanol, since these components do not completely separate from the benzene peak. A modified version of D3606 is practiced using a different internal standard and a different set of gas chromatographic columns that gives better separation of ethanol or methanol containing fuels. This modified version of the test has not been cooperatively tested by ASTM. ASTM Test Method D5580, Benzene, Toluene, Ethylbenzene, p/m-Xylene, o-Xylene, C9 and Heavier Aromatics and Total Aromatics in Finished Gasoline by Gas Chromatography, 3

20

MANUAL ON HYDROCARBON ANALYSIS


standardized tests used to determine the ignition quality of gasoline. Aviation gasolines are tested by ASTM Test Method D909, Knock Characteristics of Aviation Gasolines by the Supercharge Method. 4 Calculation of octane numbers based on compositional analysis obtained by gas chromatography has also been practiced by some companies. Octane can be predicted by using principle component regression of chromatographic data [14 ]. Today, spectroscopy techniques such as near-infrared (NIR), infrared (IR) spectroscopy, and nuclear magnetic resonance (NMR) are applied by many companies and instrument vendors for the prediction of octane numbers and other parameters of gasoline [15-18 ].

gives a detailed breakdown of the oxygenates and hydrocarbon types by carbon number. The use of supercritical fluid chromatography, (SFC), applied to gasoline analysis with a flame ionization detector, was first reported in 1984 by T. A. Norris [8 ]. Studies in Section C of ASTM D02.04 found the chromatographic column difficult to reproduce. Recent work has begun on a new multi-dimensional column approach for determining total olefins in gasoline by SFC. SFC combined with gas chromatography and or mass spectrometry has been reported giving a more detailed hydrocarbon type characterization [9,10 ]. Mass spectrometry techniques have also recently been reported for the determination of olefins in hydrocarbons or gasoline. These include the use of hydrogenation techniques and acetone chemical ionization mass spectrometry [11,12 ].

Analysis of Hydrocarbon Solvents


Although "hydrocarbon solvents" are not considered "fuels," it is appropriate to mention them because they are hydrocarbon distillates. Solvent tests are generally performed to ensure the quality of a given product as supplied by the producer to the consumer. Many solvent tests are of a somewhat empirical nature such as aniline point, ASTM Test Method D611, Aniline Point and Mixed Aniline Point of Petroleum Products and Hydrocarbon Solvents, 3 and kauributanol number, ASTM Test Method D1133, Kauri-Butanol Value of Hydrocarbon Solvents. 3 These are cited in specifications and serve a useful function as control tests. Solvent purity, however, is monitored mainly by gas chromatography, with individual non-standardized tests routinely being used by the associated industry. One method that resulted from health concerns and the need to reduce the benzene contents of solvents is ASTM Test Method D4367, Benzene in Hydrocarbon Solvents by Gas Chromatography. 3

Detailed Hydrocarbon Analysis


ASTM Test Method D5134, Detailed Analysis of Petroleum Naphthas through n-Nonane by Capillary Gas Chromatography, a is applicable to olefin-free liquid hydrocarbon mixtures including virgin naphthas, reformates, and alkylates. Higher resolution gas chromatography capillary column techniques are in routine use in petroleum laboratories today to provide a detailed analysis of most of the individual hydrocarbons in gasoline, including many of the oxygenated blending components. Software is also available that allows one to summarize the data according to hydrocarbon type and predict other parameters such as vapor pressure and distillation from the results. High-resolution GC procedures for the detailed analysis of gasoline are being considered for adoption as standard ASTM test methods. Capillary GC techniques can be combined with mass spectrometry [13 ] to enhance the identification of the individual components and hydrocarbon types.

Sulfur Content
Sulfur-containing components exist in gasoline range hydrocarbons. Individual sulfur components can be speciated using ASTM Test Method D5623, Sulfur Compounds in Light Petroleum Liquids by Gas Chromatography and Sulfur Selective Detection) This method uses a gas chromatographic capillary column coupled with either a sulfur chemiluminescence detector or atomic emission detector (AED). The total sulfur content is an important test parameter in gasoline. The most widely specified method for total sulfur content is ASTM Test Method D2622, Sulfur in Petroleum Products by X-Ray Spectrometry. 3 ASTM Test Methods D5453, Total Sulfur in Light Hydrocarbons, Motor Fuels and Oils by Ultraviolet Fluorescence, 3 and D4045, Sulfur in Petroleum Products by Hydrogenolysis and Rateometric Colorimetry, 3 are also applicable, particularly at lower sulfur levels. Studies have also been conducted in ASTM D02.03 on Elemental Analysis to improve these tests and evaluate newer methods.

FUTURE TRENDS
It is anticipated that regulations and specifications for gasoline will continue to evolve. To meet these future regulations and the changing requirements of the automotive industry, the composition of gasoline will also be changed and improved. New analytical methods will be developed to accurately test these new fuels. Petroleum-testing laboratories will apply more rapid spectroscopy techniques, faster chromatography methods, and hyphenated analytical techniques capable of measuring multiple parameters in a single analysis. More precise test methods will be implemented employing smaller sample sizes, less toxic reagents, and fewer calibration materials. The acceptance of alternative test methodologies will expand as government agencies recognize performance-based test methods for fuel analysis. In particular, the utilization and acceptance of more cost effective on-line test methods, including techniques such as NIR, FTIR, NMR, and Fiber-Optic FT Raman Spectrometry, will continue to expand [19,20 ].

Octane N u m b e r
ASTM Test Methods D2700, Motor Octane Number of Spark-Ignition Engine Fuel, 4 D2699, Research Octane Number of Spark-Ignition Engine Fuel, 4 and D2885, Research and Motor Method Octane Ratings Using On-Line Analyzers, 4 are

REFERENCES
[1 ] McCann, J. M., "ASTM Faces New Testing Challenges Created by Reformulated Gasoline Regulations," ASTM Standardization News, June 1994, pp. 23-25.

4Annual Book of ASTM Standards, Vol. 05.04.

C H A P T E R 2 - - A N A L Y S I S OF G A S O L I N E A N D O T H E R D I S T I L L A T E F U E L S
[2 ] Giarrocco, V., "Two-Minute Simulated Distillation Analysis of Gasoline Range Materials Using Short 100-/zm Diameter Caprilary Columns," Hewlett-Packard Company Application Note 228-370, Publication Number 23-5965-6416E, January 1997, Hewlett-Packard Company, Wilmington, DE. [3 ] EPA GC/OFID Method, EPA, Dec. 15, 1993, Final Rulemaking on Reformulated Gasoline. [4 ] Quimby, Giarrocco, V. and Sullivan, J., "Fast Analysis of Oxygen and Sulfur Compounds in Gasoline by GC-AED,"Journal of High Resolution Chromatography, Vol. 15, November 1992, pp. 705-709. [5 ] Diehl, J., Finkbeiner, J., and DiSanzo, F., "Determination of Ethers and Alcohols in Reformulated Gasolines by GC/AED," Journal of High Resolution Chromatography, Vol. 18, No. 2, February 1995, pp. 108-110. [6 ] DiSanzo, F. P. and Giarrocco, V. J., "Analysis of Pressurized Gasoline-Range Liquid Hydrocarbon Samples by Capillary Column and PIONA Analyzer Gas Chromatography," Journal of Chromatographic Science, Vol. 26, 1988, pp. 258-401. [7 ] EPA GC/MS Method, EPA, Dec. 15, 1993, Final Rulemaking on Reformulated Gasoline. [8 ] Norris, T. A. and Rawdon, M. G., "Determination of Hydrocarbon Types in Petroleum Liquids by Supercritical Fluid Chromatography with Flame Ionization Detection," Analytical Chemistry, Vol. 56, 1984, pp. 1767-1769. [9] Chen, E.N. Jr., Drinkwater, D.E., and McCann, J.M., "Compositional Analysis of Hydrocarbon Groups in GasolineRange Materials by Multidimensional SFC-Capillary GC," Journal of Chromatographic Science, Vol. 33, 1995, pp. 353-359. [10 ] Drinkwater, D. E., Chen, E.N. Jr., and Nero, V. P., "Direct Analysis of Fuels by Supercritical Fluid Chromatography/Mass Spectrometry," Proceedings, 44th ASMS Conference on Mass Spectrometry and Allied Topics, 1997, Portland, Oregon. [11 ] Roussis, S. G. and Fedora, J. S., "Determination of Alkenes in Hydrocarbon Matrices by Acetone Chemical Ionization Mass

21

Spectrometry," Analytical Chemist~, Vol. 97, 1997, pp. 15501556.

[12 ] Cheng, M., Hudson, J., Drinkwater, D., and Nero, V., "Total
Olefin in Gasoline Determined by Mass Spectrometry and Hydrogenation," Proceedings, 44th ASMS Conference on Mass Spectrometry and Allied Topics, 1997, Portland, Oregon. [13 ] Teng, S. T. and Williams, A. D., "Detailed Hydrocarbon Analysis of Gasoline by GC-MS (SI-PIONA)," Journal of High Resolution Chromatography, Vol. 19, 1994, pp. 469-475. [14 ] Crawford, N. F. and Hellmuth, W. W., "Refinery Octane Blend Modeling Using Principle Components Regression of Gas Chromatographic Data," Fuel, Vol. 69, 1990, pp. 443-447. [15 ] Welch, W. T., Bain, M. L., Russell, K., Maggard, S. M., and May, J. M., "Experience Leads to Accurate Design of NIR Gasoline Analysis Systems," Oil & Gas Journal, June 27, 1994, pp. 48-56. [16 ] Myers, M. E., Stollsteimer, J., and Wims, A. M., "Determination of Gasoline Octane Numbers from Chemical Composition," Analytical Chemistry, Vol. 47, No. 13, November 1975, pp. 23012304. [17 ] Ichikawa, M., Nonaka, N., Amono, H., Takada, I., Ishimori, H., Andoh, H., and Kumamoto, K., "Proton NMR Analysis of Octane Number for Motor Gasoline: Part IV," Applied Spectroscopy, Vol. 46, No. 8, 1992, p. 1294. [18 ] Andrade, J. M., Muniategui, S., and Prada, D., "Prediction of Clean Octane Numbers of Catalytic Reformed Naphthas Using FT-MIR and PLS," Fuel, Vol. 76, 1997, pp. 1035-1042. [19 ] Meusinger, R., "Gasoline Analysis by 1H Nuclear Magnetic Resonance Spectroscopy," Fuel, Vol. 75, 1996, pp. 1235-1243. [20 ] deBakker, C. J. and Fredericks, P. M., "Determination of Petroleum Properties by Fiber-Optic Fourier Transform Raman Spectrometry and Partial Least-Squares Analysis," Applied Spectroscopy, Vol. 49, No. 12, 1995, pp. 1766-1771.

Analysis of Kerosine, Diesel, and Aviation Turbine Fuel


by GregoryHemighaus
INTRODUCTION
KEROSINE, DIESEL, AND AVIATIONturbine fuel (jet fuel) are members of the class of petroleum products known as middle distillates. As the name implies, these products are heavier than gasoline but lighter than gas oils. Middle distillates cover the boiling range from approximately 175C to 375C (350F to 700F) and the carbon number range from about Cs to C24. Besides these products, gas turbine fuel, fuel oil (heating oil), and some marine fuels are also classified as middle distillates because they have a wide boiling range that overlaps the lighter fuels. These products have similar properties but different specifications as appropriate for their intended use. Methods for determining physical properties of these products are well established. They are listed in Table 2 and most will not be discussed further. Table 2 also lists methods for elemental analysis of middle distillates. This chapter will focus on compositional analysis of these products. Because of the number of isomers in this carbon number range (see Table 3), complete speciation of individual hydrocarbons is not possible for middle distillates. Compositional analysis of middle distillates is obtained in terms of hydrocarbon group type totals. These groups are most often defined by a chromatographic separation or a mass spectral Z-series.

Chromatographic Methods
The first level of compositional information is group-type totals. ASTM Test Method D1319, Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption, ~ gives volume percent saturates, olefins, and aromatics in materials that boil below 315C (600F). This covers jet fuels but not all diesel fuels, most of which have an end point above 315C. Despite this limitation, the method has been used widely for diesel fuel due to the lack of a suitable alternative. In 1988 the California Air Resources Board issued regulations that limited the aromatic content of diesel fuel sold in California starting in 1993. This heightened awareness that ASTM D1319 was not appropriate for diesel fuels led to efforts being initiated though ASTM to develop a suitable alternative. This led to the development of ASTM Test Method D5186, Determination of the Aromatic Content and Polynuclear Aromatic Content of Diesel Fuels and Aviation Turbine Fuels by Supercritical Fluid Chromatography. 1 This method does not separate saturates and olefins, so it cannot be used as a replacement for ASTM D1319. Another complication in comparing the two methods is that ASTM D1319 gives results in volume-percent while ASTM D5186 results are in mass-percent. Another approach to the determination of aromatics in middle distillates is high performance liquid chromatography, (HPLC), with refractive index (RI) detection [2 ]. The Institute of Petroleum has standardized this technique as IP-391. ASTM is currently considering this method and may adopt it as a standard. HPLC with dielectric constant detection [3 ] was considered by ASTM, but problems with detector stability prevented standardization.

CURRENT

PRACTICES

Distillation
One of the most important physical parameters defining these products is their boiling range distribution. Historically, this has been measured by ASTM Test Method D86, Distillation of Petroleum Products at Atmospheric Pressure. ASTM D86 is a low-efficiency, one theoretical plate distillation. This has been adequate for product specification purposes; however, engineering studies require true boiling point (TBP) data. TBP data can be provided by ASTM Test Method D2892, Distillation of Crude Petroleum (15-Theoretical Plate Column)J However, this method is rather difficult, time consuming, and expensive to run. TBP data are most often obtained using ASTM Test Method D2887, Boiling Range Distribution of Petroleum Fractions by Gas Chromatography ~ (simulated distillation). Use of simulated distillation has been recently reviewed [1 ].2 ~Appears in this publication. 22

Coupled Chromatographic Techniques


The combination of HPLC with GC can provide more detailed compositional information than either technique alone. Typically HPLC is used to separate a particular hydrocarbon group (saturates, mono-aromatics, di-aromatics) and transfer it to a high-resolution GC column that can resolve many of the individual compounds [4,5 ]. Supercritical fluid chromatography, (SFC), can be used instead of HPLC to make the primary separation [6 ]. These are rather sophisti2The italic face numbers in brackets refer to references at the end of this chapter.

CHAPTER 3 - - A N A L Y S I S OF KEROSINE, DIESEL, AND AVIATION TURBINE FUEL


cated techniques that are not yet suitable for routine analysis or standardization.

23

Correlative Methods
Correlative methods have long been used as a way of dealing with the complexity of petroleum fractions. Relatively easy to measure physical properties such as density, viscosity, and refractive index have been correlated to hydrocarbon composition. Several examples of this type of correlative methods are listed in Table 2. In recent years an entirely new class of correlative methods has been developed. These use near-infrared (NIR) or midinfrared spectra together with sophisticated chemometric techniques to predict a wide variety of properties. Properties such as saturates, aromatics, and freezing point of jet fuel [9 ] and density, viscosity, aromatics, heat of combustion, and cetane index of diesel fuel [10] have been successfully predicted. It is important to recognize that these methods are correlations and should not be used to estimate properties of fuels that are outside of the calibration set. There are currently no standard methods using these techniques that are applicable to middle distillates.

Spectrometric Methods
Mass spectrometry has been a powerful technique for hydrocarbon-type analysis of middle distillates. It can provide more compositional detail than chromatographic analysis. Hydrocarbon types are classified in terms of a Z-series. Z in the empirical formula CnH2n+z is a measure of the hydrogen deficiency of the compound. ASTM Test Method D2425, Hydrocarbon Types in Middle Distillates by Mass Spectrometry/ determines eleven hydrocarbon types ranging from Z = + 2 (paraffins) to Z = - 18 (tticyclic aromatics). This method requires that the sample be separated into saturate and aromatic fractions before mass spectrometric analysis. This separation is standardized as ASTM Test Method D2549, Separation of Representative Aromatics and Nonaromatics Fractions of High-Boiling Oils by Elution Chromatography. I This separation is applicable to diesel fuel but not to jet fuel, since it is impossible to evaporate the solvent used in the separation without also losing the light ends of the jet fuel. Combined gas chromatography/mass spectrometry with Townsend discharge nitric oxide chemical ionization (TDNOCI GC/MS) has been used to give similar group-type results to ASTM D2425 but without pre-separation into saturates and aromatics [7 ]. In addition, this method can give the Z series information by carbon number showing how the composition changes with boiling point. Solid phase extraction followed by capillary GC/MS has been used for detailed analysis of aromatic hydrocarbons in diesel fuel [8 ]. The percentage of aromatic hydrogen atoms and aromatic carbon atoms can be determined by ASTM Test Method D5292, Aromatic Carbon Content of Hydrocarbon Oils by High Resolution Nuclear Magnetic Resonance Spectroscopy, ~ (NMR). Results from this test are not equivalent to mass- or volume-percent aromatics determined by the chromatographic methods. The chromatographic methods determine the mass- or volume-percentage of molecules that have one or more aromatic tings. Any alkyl substituents on the rings contribute to the percentage of aromatics determined by chromatographic techniques. ASTM D5292 gives the toolpercent of aromatic hydrogen or carbon atoms. NMR can also be used to determine mass-percent hydrogen in jet fuel by ASTM Test Method D3701, Hydrogen Content of Aviation Turbine Fuels by Low Resolution Nuclear Magnetic Resonance Spectrometry, 1 and in diesel fuels by ASTM Test Method D4808, Hydrogen Content of Light Distillates, Middle Distillates, Gas Oils, and Residua by Low Resolution Nuclear Magnetic Resonance Spectroscopy. ~ Naphthalene content is an important quality parameter of jet fuel. It can be determined by ASTM Test Method D1840, Naphthalene Hydrocarbons in Aviation Turbine Fuels by Ultraviolet Spectrophotometry. ~ This method uses an average absorptivity for C~0to C~3 naphthalenes so that two fuels with the same volume-percent naphthalenes but a different distribution of isomers could give different results.

Non-Hydrocarbon Methods
Although the focus of this book is hydrocarbon analysis, heteroatoms, mainly sulfur and nitrogen compounds, cannot be ignored. Methods for determining the concentration of these elements are well established and listed in Table 2. The combination of gas chromatography with element selective detection gives information about the distribution of the element. In addition, many individual heteroatomic compounds can be determined. Selective sulfur and nitrogen GC detectors, exemplified by the flame photometric detector (FPD) and the nitrogenphosphorus detector (NPD), have been available for many years. However, these detectors have limited selectivity for the element over carbon, exhibit non-uniform response, and have other problems that limit their usefulness. A new generation of element selective detectors has become available based on chemiluminescence and plasma emission spectroscopy that have excellent sensitivity, uniformity of response, and selectivity over carbon. Nitrogen compounds in middle distillates can be selectively detected by chemiluminescence [11 ]. Individual nitrogen compounds can be detected down to 100 ppb nitrogen. Gas chromatography with either sulfur chemiluminescence detection [12 ] or atomic emission detection [13 ] has been used for sulfur selective detection.

FUTURE TRENDS
The trend toward more detailed compositional information is expected to continue. The combination of multiple chromatographic separations and spectroscopic detection is a very powerful approach to the analysis of complex petroleum fractions. The mass spectrometry group-type methods, including ASTM D2425, were developed on magnetic sector instruments that are no longer in use. ASTM is working on updat-

24

MANUAL ON HYDROCARBON ANALYSIS


leum Fractions," Journal of Chromatographic Science, Vol. 32, 1994, pp. 534-540. [7 ] Dzidic, I., Petersen, H. A., Wadsworth, P. A., and Hart, H. V., "Townsend Discharge Nitric Oxide Chemical Ionization Gas Chromatography/Mass Spectrometry for Hydrocarbon Analysis of the Middle Distillates," Analytical Chemistry, Vol. 64, 1992, pp. 2227-2232. [8 ] Bundt, J. et al., "Structure-Type Separation of Diesel Fuels by Solid Phase Extraction and Identification of the Two- and Three-Ring Aromatics by Capillary GC-Mass Spectrometry," Journal of High Resolution Chromatography, Vol. 14, 1991, pp. 91-98. [9 ] Lysaght, M. A., Kelly, J. J., and Callis, J. B., "Rapid Spectroscopic Determination of Percent Saturates and Freezing Point of JP-4 Aviation Fuel," Fuel, Vol. 72, 1993, pp. 623-631. [10 ] Fodor, G.E. and Kohl, K. B., "Analysis of Middle Distillate Fuels by Midband Infrared Spectroscopy," Energy and Fuels, Vol. 7, 1993, pp. 598-601. [11 ] Chawha, B., "Speciation of Nitrogen Compounds in Gasoline and Diesel Range Process Streams by Capillary Column Gas Chromatography with Chemiluminescence Detection," Journal of Chromatographic Science, Vol. 35, 1997, pp. 97-104. [12 ] Kabe, T., Ishihara, A., and Tajima, H., "Hydrodesulfurization of Sulfur-Containing Polyaromatic Compounds in Light Oil," Industrial Engineering Chemistry Research, Vol. 31, 1992, pp. 1577-1580. [13] Hutte, R. S., "Chromatography in the Petroleum Industry," Journal of Chromatography Library Series, E. R. Adlard, Ed., Vol. 56, 1995, Elsevier, New York.

ing these methods to be used on m o d e r n quadrupole mass spectrometers. The ability to rapidly predict m a n y fuel properties suggests that the infrared/chemometric correlative techniques m a y find their best applications in on-line process control rather t h a n in the laboratory.

REFERENCES
[1 ] Abbott, D.J., "Chromatography in the Petroleum Industry," Journal of Chromatography Library Series, E. R. Adlard, Ed., Vol. 56, 1995, Elsevier, New York. [2 ] Sink, C. W. and Hardy, D. R., "Quantification of Compound Classes in Complex Mixtures and Fuels Using HPLC with Differential Refractive Index Detection," Analytical Chemistry, Vol. 66, 1994, pp. 1334-1338. [3 ] Hayes, P. C., Jr. and Anderson, S. D., "The Analysis of Hydrocarbon Distillates for Group Types Using HPLC with Dielectric Constant Detection: A Review," Journal of Chromatographic Science, Vol. 26, 1988, pp. 210-217. [4 ] Trisciani, A. and Munari, F., "Characterization of Fuel Samples by On-Line LC-GC with Automatic Group-Type Separation of Hydrocarbons," Journal of High Resolution Chromatography, Vol. 17, 1994, pp. 452-456. [5 ] Kelly, G. W. and Bartle, K. D., "The Use of Combined LC-GC for the Analysis of Fuel Products: A Review," Journal of High Resolution Chromatography, Vol. 17, 1994, pp. 390-397. [6 ] Lynch, T. P. and Heyward, M. P., "Coupled Packed SFC and Capillary GC for the Quantitative Analysis of Complex Petro-

Analysis of Viscous Oils


by Thomas M. Warne
INTRODUCTION
VISCOUSOILSare those petroleum fractions and derived products that have higher boiling points than distillate fuels and are liquid at, or slightly above, room temperature. They contain 20 to 50+ carbon atoms and distill at temperatures above 260C (500F). Examples include refinery streams such as gas oils and residuum, heavier fractions obtained from refining processes such as catalytic cracking, reforming, polymerization, solvent extraction, and hydro- and thermal cracking. Viscous oils include finished products such as lubricants, process oils, and insulating oils. Asphalt and coke are discussed only incidentally. These hydrocarbons are important commercially, providing both finished products for sale and feedstocks for further processing, primarily to fuels. The hydrocarbon composition of the viscous oils and the presence of heteroatoms and metals as contaminants or additives are the major determinant of the quality of finished products prepared from them. Detailed analysis of viscous oils is far more complex than the analysis of hydrocarbon gases and lower molecularweight liquids. The number of types of molecules present increases rapidly as the number of carbon atoms per molecule increases. Hydrocarbons in the viscous oil range are generally extremely complex mixtures. Characterization does not focus on identifying specific molecular structures, but on classes of molecules (paraffins, naphthenes, aromatics, polycyclic compounds, polar compounds, etc.). Besides complexity, analysis of viscous oils may be complicated by handling problems. The higher viscosity of the fluids makes them more difficult to sample and transfer. Many viscous oils have a very dark color, which causes problems with some test methods. Finally, besides carbon and hydrogen, high molecular weight fractions of crude oil often contain oxygen, sulfur, and nitrogen compounds; trace quantities of metals may also be present. Determining the chemical form present for these elements provides additional important information. Finished products made using viscous oils may contain additives or contaminants that also require analysis. range; those methods that are used to measure chemical composition such as elemental and molecular structure analysis; and derivative methods that correlate measured properties with aspects of chemical composition.

Physical Tests
Density (Gravity)
Density or relative density (specific gravity) is used whenever conversions must be made between mass (weight) and volume measurements. This property is often used in combination with other test results to predict oil quality. Five ASTM procedures for measuring density or gravity are generally applicable to measurements on viscous oils. ASTM Test Method D287, API Gravity of Crude Petroleum and Petroleum Products (Hydrometer Method)/ and ASTM Practice D1298, Density, Relative Density (Specific Gravity), or API Gravity of Crude Petroleum and Liquid Petroleum Products by Hydrometer Method, t use an immersed hydrometer for measurement. ASTM D287 is a special case of the hydrometer method that provides results as API gravity. Two other ASTM Test Methods, D1480, Density and Relative Density (Specific Gravity) of Viscous Materials by Bingham Pyncnometer, 2 and D1481, Density and Relative Density of Viscous Materials by Lipkin Bicapillary Pycnometer, 2 use a pycnometer to measure density or specific gravity and have the advantage of requiring a smaller sample size. Finally, ASTM Test Method D4052, Density and Relative Density of Liquids by Digital Density Meter 1 (and the related ASTM Test Method D5002, Density and Relative Density of Crude Oils by Digital Density Analyzer)/ measure density with a digital density analyzer. This device, which has gained wide acceptance, determines density by analysis of the change in oscillating frequency of a sample tube when filled with test oil. Viscous oils generally do not create problems because of sample volatility; however, all of the test methods are sensitive to the presence of gas bubbles in the fluid. With viscous oils, particular care must be taken to exclude or remove gas bubbles before measurement. With dark-colored samples, it may be difficult to determine whether all air bubbles have been eliminated. ~Appears in this publication. 2Annual Book of ASTM Standards, Vol. 05.01.

C U R R E N T PRACTICES
Test methods of interest for hydrocarbon analysis of viscous oils include tests that measure physical properties such as density, refractive index, molecular weight, and boiling

25

26

MANUAL ON HYDROCARBON ANALYSIS


Other approaches to determining molecular weight include distillation (gas chromatography) and mass spectroscopy. These are discussed separately.

Refractive Index
Refractive index is the ratio of the velocity of light in air to the velocity of light in the measured substance. The numerical value of the refractive index varies inversely with the wavelength of light used and the temperature at which the measurements are taken. The refractive index of a substance is related to its chemical composition and may be used to draw conclusions about molecular structure. Two ASTM test methods are available for measuring the refractive index of viscous liquids. Both methods are limited to lighter-colored samples for best accuracy. Both methods were written for instruments which are no longer manufactured. ASTM Test Method D 1218, Refractive Index and Refractive Dispersion of Hydrocarbon Liquids/ is designed to use the Bausch & Lomb Precision Refractometer. This model is no longer manufactured. ASTM Test Method D 1747, Refractive Index of Viscous Materials,~ uses the Abbe type (Valentine) refractometer, which is no longer made. In both cases, other refractometers are available, but no cooperative work has been conducted to verify equivalence. There are also limitations on the availability of thermometers with suitable range and accuracy that will fit the instruments. ASTM Subcommittee D02.04.0D plans cooperative testing of modern commercial refractometers to develop precision data, but data are not yet available.

Distillation
Four distillation methods are in common use for determining the boiling range and for collecting fractions from viscous oils. ASTM Test Method D1160, Distillation of Petroleum Products at Reduced Pressure, 1 is probably the best known and most widely used of the methods for distillation of higherboiling petroleum products. The method is a vacuum distillation, applicable to samples that can be at least partially volatilized at temperature up to 400C and pressure in the range 1 to 50 mm Hg. The distillation temperature at vacuum is converted to atmospheric equivalent temperatures. ASTM Test Method D447, Distillation of Plant Spray Oils/ is a method designed for characterization of these narrowboiling fractions. (Optimal persistence with minimal damage to plant fruit and foliage is obtained when narrow boiling petroleum fractions of appropriate volatility are used.) ASTM Test Method D2892, Distillation of Crude Petroleum (15-Theoretical Plate Column)/ applies to a wide range of products. The procedure uses a column with 15 theoretical plates and a 5"1 reflux ratio. The distillation is started at atmospheric pressure until the vapor temperature reaches 210C. Distillation is continued at vacuum (100 mm Hg) until the vapor temperature again reaches 210C or cracking is observed. With very heavy crudes or viscous products, a preferred alternate distillation method is ASTM Test Method D5236, Distillation of Heavy Hydrocarbon Mixtures (Vacuum Potstill Method). 1 This method should be used instead of ASTM D2892 for heavy crudes above a 400C cutpoint. Unless a distillation method is required by specification or the collected fractions are needed for further testing, gas chromatographic methods have become preferred for determining the boiling range of petroleum fractions. ASTM Test Method D2887, Boiling Range Distribution of Petroleum Fractions by Gas Chromatography/ gives detailed information for samples with a final boiling point no higher than 538C (1000F) at atmospheric pressure and a boiling range greater than 55C (100F). Some laboratories have used modified procedures to analyze fractions boiling higher than 538C. ASTM Subcommittee D02.04 has prepared a draft method that covers products boiling to 838C; this method should be standardized in the near future.

Molecular Weight
Since viscous oils are commonly broad-boiling mixtures, measurements of molecular weight commonly provide massaverage or number-average measurements. A variety of methods are available. Molecular weight may be calculated from viscosity data using ASTM Test Method D2502, Estimation of Molecular Weight (Relative Molecular Mass) of Petroleum Oils from Viscosity Measurements. ~The current version requires centistoke viscosity at 100 and 210F. The method is generally applicable to "average" petroleum fractions with molecular weight in the range 250 to 700. Samples with unusual composition, such as aromatic-free white mineral oils, or oils with very narrow boiling range, may give atypical results. For samples with higher molecular weight (up to 3000 or more) with unusual composition or for polymers, ASTM Test Method D2503, Relative Molecular Mass (Molecular Weight) of Hydrocarbons by Thermoelectric Measurement of Vapor Pressure, ~ is recommended. This method uses a vapor pressure osmometer to determine molecular weight. Low boiling samples may not be suitable if their vapor pressure interferes with the method. The method has only been standardized by ASTM for samples up to a molecular weight of 800. A third method is also available. ASTM Test Method D2878, Estimating Apparent Vapor Pressures and Molecular Weights of Lubricating Oils, ~ provides a procedure to calculate these properties from test data on evaporation. The procedure is based on ASTM Test Method D972, Evaporation Loss of Lubricating Greases and Oils.I The sample is partly evaporated at a temperature of 250 to 500C; fluids not stable in this temperature range may require special treatment [1]. 3 3The italic numbers in brackets refer to the list of references at the end of this chapter.

Chemical Composition
Elemental Analysis
In elemental analysis of viscous oils, the analyst is most commonly interested in the presence of contaminant metals, nitrogen, and sulfur present in the hydrocarbon fraction. For finished products, additional information is sought regarding elements contributed by additives. While there exist many classical, wet chemical methods for determination of metals and certain elements, routine analysis generally involves instrumental methods based on spectrometric techniques including atomic absorption, emission, X-ray and plasma spectrometry.

C H A P T E R 4 - - A N A L Y S I S OF V I S C O U S O I L S
Carbon and hydrogen are commonly determined by combustion analysis. There are numerous commercial instruments designed for this purpose. Generally, the sample is burned in an oxygen stream where carbon is converted to carbon dioxide and hydrogen to water. These compounds are absorbed and the composition is determined automatically from mass increase. Some instruments also measure nitrogen. ASTM Test Method D5291, Instrumental Determination of Carbon, Hydrogen and Nitrogen in Petroleum Products and Lubricants, 1 is a guide that summarizes general instructions to supplement manufacturers' instructions for their apparatus. It includes a list of recommended calibration standards for carbon, hydrogen, and nitrogen analyses.

27

Sulfur may also be determined along with metals by using ASTM Test Methods D4927, D4951, or D5185. These methods are described below under "Metals."

Nitrogen
Nitrogen is present in viscous oils primarily as amines and heterocyclic ring compounds. Nitrogen is also a component of many additives used in petroleum products, including oxidation and corrosion inhibitors and dispersants. There are four ASTM standards describing analytical methods for nitrogen in viscous oils. ASTM Test Method D3228, Total Nitrogen in Lubricating Oils and Fuel Oils by Modified Kjeldahl Method, 4 is a standard wet chemical method. It is useful for determining the nitrogen content of most viscous oils in the range from 0.03 to 0.10 mass-%. The other three methods are instrumental techniques; one involves nitrogen reduction, the other two nitrogen oxidation. ASTM Test Method D3431, Trace Nitrogen in Liquid Petroleum Hydrocarbons (Microcoulometric Method), 5 is an instrumental method where nitrogen is pyrolyzed under reducing conditions and converted to ammonia, which is measured coulometrically. This method is very useful in assessing feeds for catalytic hydrogenation processes where nitrogen may act as a catalyst poison. ASTM Test Method D4629, Trace Nitrogen in Liquid Petroleum Hydrocarbons by Syringe/Inlet Oxidative Combustion and Chemiluminescence Detection/ is useful for samples containing 0.3 to 100 ppm nitrogen and boiling higher than 400C but with viscosities of 10 cSt or less. Organic nitrogen is converted to NO and then to excited NO2 by reaction with oxygen and then ozone. Energy emitted during decay of the excited NO2 is measured with a photomultiplier tube. ASTM Test Method D5762, Nitrogen in Petroleum and Petroleum Products by Boat-Inlet Chemiluminescence, ~ is a complementary method suitable for more viscous samples that contain from 40 to 10,000 ppm nitrogen.

Sulfur
Sulfur is naturally present in many crude oils and petroleum fractions, most commonly as organic sulfides and heterocyclic compounds. Many refining steps aim to reduce this sulfur content to improve stability and reduce environmentally harmful emissions. Sulfur is also a component of wear-reducing and load-carrying additives, corrosion inhibitors, detergents, and emulsifiers. The methods used to measure sulfur content vary depending on the sulfur concentration, viscosity or boiling range, and presence of interfering elements. ASTM Test Method D129, Sulfur in Petroleum Products (General Bomb Method), 2 uses sample combustion in oxygen and conversion of the sulfur to barium sulfate, which is determined by mass. This method is suitable for samples containing 0.1 to 5.0 mass-% sulfur and can be used for most low-volatility petroleum products. Elements that produce residues insoluble in hydrochloric acid interfere with this method--this includes aluminum, calcium, iron, lead, and silicon, plus minerals such as asbestos, mica, and silica. For such samples, ASTM Test Method D1552, Sulfur in Petroleum Products (High Temperature Method), ~ is preferred. This method describes three procedures: the sample is first pyrolyzed in either an induction furnace or a resistance furnace; the sulfur is then converted to sulfur dioxide and either titrated with potassium iodate-starch reagent or the sulfur dioxide is analyzed by infrared spectroscopy. This method is generally suitable for samples containing from 0.06 to 8.0 mass-% sulfur and that distill at temperatures above 177C. Two methods describe the use of X-ray techniques for sulfur determination. ASTM Test Method D2622, Sulfur in Petroleum Products by X-Ray Spectrometry, ~ can be used for samples with sulfur content of 0.001 to 5.0 mass-%. ASTM Test Method D4294, Sulfur in Petroleum Products by EnergyDispersive X-Ray Fluorescence Spectroscopy/ is useful at sulfur concentrations of 0.05 to 5.0 mass-%. Oil viscosity is not a critical factor with these two methods, but interference may affect test results when chlorine, phosphorus, heavy metals, and possibly silicon are present. For very low sulfur concentrations, a method that may be used is ASTM Test Method D4045, Sulfur in Petroleum Products by Hydrogenolysis and Rateometric Colorimetry? This is normally used for lower-viscosity fractions, but may be used for some viscous oils that boil below 371C. The method is designed to measure sulfur in the range 0.02 to 10 mass-ppm.

Metals
The viscous fractions of crude oil often contain heavy metals such as iron, nickel, and vanadium. Catalytic refining processes are often sensitive to metal contamination and, therefore, the type and quantity of metals must be determined. In other cases such as lubricating oils, some metals are parts of compounds added to the petroleum component to enhance performance. Quantitative analysis for these metals is an important quality control step. ASTM Test Method D811, Chemical Analysis for Metals in New and Used Lubricating Oils, 6 is a standard wet cb_emical analysis method for aluminum, barium, calcium, magnesium, potassium, silicon, sodium, tin, and zinc. The procedure involves a series of chemical separations with specific elemental analysis performed using appropriate gravimetric or volumetric analyses. The method is very labor-intensive and is used primarily as a referee method or to calibrate standards for instrumental methods.

4Annual Book of ASTM Standards, Vol. 05.02. 5Discontinued; see 1993 Annual Book of ASTM Standards, Vol. 05.02. 6Discontinued; see 1989 Annual Book of ASTM Standards, Vol. 05.01.

28

MANUAL ON HYDROCARBON ANALYSIS


the organic material and dissolve the metals or, alternatively, the sample is dissolved in an organic solvent. The second procedure measures oil-soluble metals only and not insoluble particles. This inability to accurately measure metals in larger particles is true for many related methods. The method is sensitive down to about 1 ppm; the precision statement is based on samples containing i to 10 ppm iron, 10 to 100 ppm nickel, or 50 to 500 ppm vanadium. Finally, a second method provides an alternate method for analysis of crude oils and residuum: ASTM Test Method D5863, Determination of Nickel, Vanadium, Iron and Sodium in Crude Oils and Residual Fuels by Flame Atomic Absorption Spectrometry. 1 Pretreatment and limitations on determination of insoluble materials are identical to ASTM D5708. The sensitivity range is 3.0 to 10 ppm for iron, 0.5 to 100 ppm for nickel, 0.1 to 20 ppm for sodium, and 0.5 to 500 ppm for vanadium. Higher concentrations may be determined after dilution.

The most commonly used methods for determining metal content in viscous oils are spectroscopic techniques. Six ASTM standard methods exist that are applicable to viscous oils. Most methods permit simultaneous analysis of several elements; commercial instruments are readily available. Two use atomic absorption, one uses X-ray fluorescence, and three use inductively coupled plasma (ICP) spectroscopy. ASTM Test Method D4628, Analysis of Barium, Calcium, Magnesium and Zinc in Unused Lubricating Oils by Atomic Absorption Spectrometry, 1 is designed primarily for quality control analysis of additive metals in finished lubricants. The sample is diluted in kerosine and burned in an acetylenenitrous oxide flame of an AA spectrophotometer. The method is suitable for oils in the lubricating oil viscosity range. It is designed to measure barium at concentrations of 0.005 to 1.0 mass-%, calcium and magnesium at 0.002 to 0.3 mass-%, and zinc at 0.002 to 0.2 mass-%. Higher metal concentrations, such as are present in additives, can be determined by dilution. Lower concentrations in the range of 10 to 50 ppm can also be determined; however, the precision is poorer. An alternate test method is ASTM Test Method D4927, Elemental Analysis of Lubricant and Additive Components--Barium, Calcium, Phosphorus, Sulfur and Zinc by WavelengthDispersive X-Ray Fluorescence Spectroscopy. ~ The techniques are designed for unused lube oils containing metals at concentration levels from 0.03 to 1.0 mass-% and sulfur at 0.01 to 2.0 mass-%. Higher concentrations can be determined after dilution. A third technique is ASTM Test Method D4951, Determination of Additive Elements in Lubricating Oils by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP/AES). 1 Determined elements are barium, boron, calcium, copper, magnesium, phosphorus, sulfur, and zinc in unused lubricating oils and additive packages. Elements can generally be determined at concentrations of 0.01 to 1.0 mass-%. The sample is diluted in mixed xylenes or other solvents containing an internal standard. ASTM Test Method D5185, Determination of Additive Elements, Wear Metals and Contaminants in Used Lubricating Oils and Determination of Selected Elements in Base Oils by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP/AES),~ describes a modified ICP method. Although these methods are designed for used lubricating oils, they are also applicable to unused oils. Sensitivity and useable range varies from one element to another, but the method is generally applicable from 1 to 100 ppm for contaminants and up to 1000 to 9000 ppm for additive elements. The method covers: Additive Elements calcium magnesium phosphorus potassium sulfur zinc Contaminant Elements lead sodium manganese tin molybdenum titanium nickel vanadium silicon silver

Miscellaneous E l e m e n t s
Chlorine is present in some metalworking fluids as a chlorinated hydrocarbon or ester. It is less common in other viscous oils, but may be present in crude oils from brine contamination. Chlorine in lubricating oils can be determined using ASTM Test Method D808, Chlorine in New and Used Petroleum Products (Bomb Method), 2 or ASTM Test Method D1317, Chlorine in New and Used Lubricants (Sodium Alcoholate Method). 7 A rapid test method suitable for analysis of samples by non-technical personnel is ASTM Test Method D5384, Chlorine in Used Petroleum Products (Field Test Kit Method)? This method uses a commercial test kit where the oil sample is reacted with metallic sodium to convert organic halogens to halide, which is titrated with mercuric nitrate using diphenyl carbazone indicator. Iodides and bromides are reported as chloride. A special concern is contamination of viscous oils with polychlorinated biphenyls (PCBs). Electrical insulating oils require analysis before disposal to ensure the absence of PCBs. ASTM Test Method D6160, Determination of Polychlorinated Biphenyls (PCBs) in Waste Materials by Gas Chromatography, ~ is a newly introduced and widely applicable method. Standard reference samples for nine commercial PCBs (Aroclors) are available. Phosphorus is a common component of lubricating oil additives. It appears most commonly as a zinc dialkyl dithiophosphate or a tri-aryl phosphate ester, but other forms also occur. Two wet chemical methods are available. ASTM Test Method D1091, Test Methods for Phosphorus in Lubricating Oils and Additives, 2 describes an oxidation procedure that converts phosphorus to aqueous ortho-phosphate anion. This is then determined by mass as magnesium pyro-phosphate or photochemically as molybdi-vanadophosphoric acid. Phosphorus concentrations of 0.0002 to 20.0 mass-% can be accommodated by these procedures. An alternate test is ASTM Test Method D4047, Phosphorus in Lubricating Oils and Additives by Quinoline Phosphomolybdate Method. 4 Samples are oxidized to phosphate with zinc oxide, dissolved in acid, precipitated as quinoline phosphomolybdate, treated with excess standard alkali, and back-titrated with standard 7Discontinued; see 1994 Annual Book of ASTM Standards, Vol. 05.01.

aluminum barium boron chromium copper iron

A third ICP method is ASTM Test Method D5708, Determination of Nickel, Vanadium and Iron in Crude Oils and Residual Fuels by Inductively Coupled Plasma (ICP) Atomic Emission Spectrometry. I Two procedures are described whereby the sample is either treated with acid to decompose

CHAPTER 4--ANALYSIS OF VISCOUS OILS


acid. Both of these methods are primarily used for referee samples. Phosphorus is most commonly determined using X-ray fluorescence or ICP by ASTM Test Methods D4927 or D4951, which have been described previously under Metals.

29

mixture during processing. They are less reliable when comparing materials of different origin and can be very misleading when applied to atypical or unusual compositions.

Chromatography
A major use for gas chromatography for hydrocarbon analysis has been simulated distillation, as discussed previously. Other gas chromatographic methods have been developed for contaminant analysis. These include: ASTM Test Methods D3524, Diesel Fuel Diluent in Used Diesel Engine Oils by Gas Chromatography,1 and D4291, Trace Ethylene Glycol in Used Engine Oil. Column chromatography is used for several hydrocarbon type analyses that involve fractionation of viscous oils. Examples are: ASTM Test Methods D2007, Characteristic Groups in Rubber Extender and Processing Oils and Other Petroleum-Derived Oils by the Clay-Gel Absorption Chromatographic Method/ and D2549, Separation of Representative Aromatics and Nonaromatics Fractions of High-Boiling Oils by Elution Chromatography.~ ASTM D2007 uses absorption on clay and clay-silica gel, followed by elution of the clay with pentane to separate saturates; elution of clay with acetonetoluene to separate polar compounds; and elution of the silica gel fraction with toluene to separate aromatic compounds. ASTM D2549 uses absorption on a bauxite-silica gel column. Saturates are eluted with pentane; aromatics are eluted with ether, chloroform, and ethanol. A new method for hydrocarbon type analysis using supercritical fluid chromatography is under development by ASTM Subcommittee D02.04 and should be available shortly. Several promising chromatographic techniques have been reported for the analysis of lubricant base oils. Rod thin layer chromatography (TLC), high-performance liquid chromatography (HPLC), and supercritical fluid chromatography (SFC) have all been used for base oil analysis and base oil content [3-6 ]. Work to develop test methods is underway. Chromatographic methods are also extremely useful for isolation and identification of lubricant additives. Some recent papers reporting these techniques are available [7-9 ]. These methods have not yet been developed as standardized procedures.

Hydrocarbon Structure
Compositional analysis is concerned with determining structural relationships in the molecules present in a sample. Infrared spectroscopy is the most commonly used tool for qualitative chemical analysis of viscous oils. Descriptions and tables of characteristic absorbance for a variety of organic functional groups are readily available in many textbooks. Techniques for quantitative analysis for many additives and some hydrocarbon types are available, although few have been issued as ASTM standards. Reports on new methods are commonly reported in the chemistry literature. To locate information on new analytical methods, a most useful reference is the bi-annual Application Review published by the American Chemical Society. These have appeared recently in the June 15 issue of Analytical Chemistry in odd-numbered years. Recent reviews cover coal, crude oil, shale oil, heavy oils (natural and refined), lubricants, natural gas, and refined products and source rocks. Extensive references to original research papers are provided. A complimentary Fundamental Review covering the basic analytical techniques is published in even-numbered years. This review will emphasize those methods standardized by ASTM or under study within the committee.

Correlative Methods
Correlative methods are derived relationships between fundamental chemical properties of a substance and measured physical or chemical properties. They provide information about an oil from readily measured properties. Examples of correlative methods of use with viscous oils are: ASTM Test Methods D2140, Carbon Type Composition of Insulating Oils of Petroleum Origin; a D2501, Calculation of Viscosity-Gravity Constant (VGC) of Petroleum Oils; ~D2502, Estimation of Molecular Weight (Relative Molecular Mass) of Petroleum Oils from Viscosity Measurements; ~ and D3238, Calculation of Carbon Distribution and Structural Analysis of Petroleum Analysis by the n-d-M Method. 4 D2501 describes the calculation of the viscosity-gravity coefficient. The VGC is a parameter derived from kinematic viscosity and density that has been found [2 ] to relate to the saturate/aromatic composition. D2502 permits estimation of molecular weight from kinematic viscosity measurements. This can be used with other properties to characterize hydrocarbon mixtures. ASTM D2140 and D3238 use correlations between the viscosity-gravity coefficient (or molecular weight and density) and refractive index to calculate carbon type composition in percent of aromatic, naphthenic, and paraffinic carbon atoms and an estimate of the number of aromatic and naphthenic rings present. Data from correlative methods must not be confused with more fundamental measurements obtained by chromatography or mass spectroscopy. Correlative methods can be extremely useful when used to follow changes in a hydrocarbon

Spectrometric Methods
Perhaps the most commonly used spectrometric method for analysis of viscous oils is infrared spectroscopy. General instructions for qualitative hydrocarbon type and functional group analysis are widely available. Papers have also been published for quantitative analysis of hydrocarbon types [10]. FT-IR techniques have been reported for use in predictive maintenance programs to monitor the concentration of additives and degradation products in used oils [11 ]. Two methods have been standardized using NMR for hydrocarbon characterization. An alternative to ASTM D5291 for determining hydrogen content of viscous oils is ASTM Test Method D4808, Hydrogen Content of Light Distillates, Middle Distillates, Gas Oils and Residua by Low Resolution Nuclear Magnetic Resonance Spectroscopy? The NMR method is simpler and more precise than techniques previously described in ASTM D5291. Procedures are described that cover light distillates with a 15 to 260C boiling range, middle distillates and gas oils with boiling ranges of 200 to 370C and 370 to 510C, and residuum boiling above 510C.

8Annual Book of ASTM Standards, Vol. 10.03.

30

MANUAL ON H YD R O C A R B O N A N A L Y S I S
constantly available. This t r e n d is expected to continue. A m a j o r challenge is to m a t c h s t a n d a r d test m e t h o d s with new e q u i p m e n t so that m e t h o d s do not b e c o m e obsolete. C o m b i n i n g s e p a r a t i o n a n d analysis techniques (hyphena t e d techniques) can p r o d u c e powerful tools for characterizing viscous oils. Thus, liquid c h r o m a t o g r a p h y o r gas c h r o m a t o g r a p h y can be used to s e p a r a t e a s a m p l e for subsequent c h a r a c t e r i z a t i o n by m a s s s p e c t r o m e t r y (LC/MS o r GC/MS). Research into suitable m e t h o d s for the analysis of viscous oils is underway, b u t no s t a n d a r d tests have yet b e e n prepared. Extensive r e s e a r c h on b o t h p r o t o n a n d carbon-13 nuclear m a g n e t i c r e s o n a n c e s p e c t r o s c o p y shows p r o m i s e as a tool for the analysis of lubricant base oils and other viscous oils. Both n e a r - i n f r a r e d spectroscopy (NIR) a n d F o u r i e r - t r a n s f o r m IR (FTIR) are the subjects of active research into m e t h o d s to characterize h y d r o c a r b o n s a n d for quality control d u r i n g p r o d u c t i o n of p e t r o l e u m products. S t a n d a r d test m e t h o d s using these techniques should b e c o m e available in the future.

ASTM Test M e t h o d D5292, A r o m a t i c C a r b o n Contents of H y d r o c a r b o n Oils b y High Resolution N u c l e a r Magnetic Reso n a n c e Spectroscopy, 1 p e r m i t s d e t e r m i n a t i o n of a r o m a t i c h y d r o g e n a n d a r o m a t i c c a r b o n content of gas oils, lubricating oils, a n d other h y d r o c a r b o n fractions that are completely soluble in c h l o r o f o r m a n d c a r b o n t e t r a c h l o r i d e at a m b i e n t t e m p e r a t u r e s . Concentrations as low as 0.1 mol-% h y d r o g e n a n d 0.5 mol-% c a r b o n can be d e t e r m i n e d . Olefins a n d p h e n o lic c o m p o u n d s above 1 mass-% interfere. ASTM C o m m i t t e e D02 has s t a n d a r d i z e d three m e t h o d s for h y d r o c a r b o n c o m p o s i t i o n a l analysis using m a s s spectrometry. One of these is ASTM Test M e t h o d D2786, H y d r o c a r b o n Types Analysis of Gas-Oil S a t u r a t e s F r a c t i o n s by High Ionizing Voltage Mass S p e c t r o m e t r y ? A c o m p l e m e n t a r y m e t h o d is ASTM Test M e t h o d D3239, A r o m a t i c Types Analysis of Gas-Oil Aromatic F r a c t i o n s by High Ionizing Voltage Mass Spectrometry.1 These m e t h o d s require p r e l i m i n a r y sepa r a t i o n using elution c h r o m a t o g r a p h y , ASTM D2549, or similar method. A third m e t h o d , ASTM Test Method D2425, H y d r o c a r b o n Types in Middle Distillates by Mass Spectromet r y / m a y be applicable to s o m e viscous oil samples in the lower m o l e c u l a r weight range. The p r o c e d u r e s used in these m e t h o d s were originally developed a n d r e p o r t e d in 1969 [12 ]. They were developed using the Consolidated E l e c t r o d y n a m i c s Corp. Type 103 series (Model 21-100 a n d later the DuPont 21-103 a n d 21-104 instruments). These i n s t r u m e n t s are no longer in production. While n e w e r i n s t r u m e n t s are r e p o r t e d to give satisfactory results, the p r o c e d u r e s for their use have not been s t a n d a r d ized. Efforts are now in progress to provide test m e t h o d s using newer, lower-cost instruments. The use of q u a d r u p o l e i n s t r u m e n t s a n d a c o m b i n a t i o n of m a s s spectroscopy with gas or liquid c h r o m a t o g r a p h y should p r o d u c e useful new procedures.

REFERENCES
[1 ] Coburn, J. F, "Lubricant Vapor Pressure Derived From Evaporation Loss," Transactions, American Society of Lubricating Engineers, ASLTA, Vol. 12, 1969, pp. 129-134. [2 ] Coats, H. B. and Hill, J. B., Industrial & Engineering Chemist~, Vol. 20, 1928, p. 641. [3 ] Barman, B. N., Journal of Chromatographic Science, Vol. 34, No. 5, 1996, pp. 219-225. [4 ] Sassiat, P. et al., Anal. Chim. Acta, Vol. 306, No. 1, 1995, pp. 73-79. [5 ] Kagdiyal, R. et al., Proceedings, Adv. Prod. Appl. Lube Base Stocks, 1994, pp. 295-302. [6 ] Jain, M. C. et al., Adv. Prod. Appl. Lube Base Stocks, 1994, pp. 272-279. [7] Hui, R. and Rosset, R.,Anal. Chim. Acta, Vol. 314, No. 3, 1995, pp. 1650-1657. [8 ] Machtalere, G. et al., Anal. Chim. Acta, Vol. 322, Nos. 1-2, 1996, pp. 31-41. [9 ] Lambroupoulos, N. et al., Journal of Chromatography, Vol. 749, Nos. 1-2, 1996, pp. 87-94. [10 ] Brandes, G., Brennstoff-Chemie, Vol. 37, 1956; Erdol und Kohle, Vol. 11, No. 10, 1958. [11 ] Powell, J. R. and Compton, D. A. C., Lub Eng., Vol. 49, No. 3, 1993, pp. 233-239. [12 ] Robinson, C. J. and Cook, G. L., Analytical Chemistry A, Vol. 41, 1969, p. 1548 ft.

FUTURE TRENDS
As n o t e d in previous editions, the t r e n d in h y d r o c a r b o n analysis is away from m a n u a l test m e t h o d s a n d increasingly favors a u t o m a t e d i n s t r u m e n t a l methods. C o m m e r c i a l instrum e n t s are available that will p e r f o r m m a n y of the p r o c e d u r e s d e s c r i b e d in this chapter. While ASTM c o m m i t t e e s have stand a r d i z e d tests b a s e d on s o m e of these instruments, c o m m e r cial d e v e l o p m e n t is r a p i d a n d new analytical i n s t r u m e n t s are

Analysis of Waxes
by Arthur D. Barker
INTRODUC~ON
PETROLEUM WAXES are the solid hydrocarbon residues remaining at the end of the refining process either in the lube stream (as mainly paraffin and intermediate waxes) or in the residual lube stock "tank bottoms" (as higher melting microcrystalline waxes). The waxy oil is fractionated to produce an oily wax, called slackwax. This is separated by solvent extraction and fractionated into different melting point ranges to give waxes with a variety of physical characteristics. Paraffin waxes consist mainly of straight chain alkanes (also called normal alkanes), with small amounts (3 to 15%) of branched chain alkanes (or iso-alkanes), cycloalkanes, and aromatics. Microcrystalline waxes contain high levels of branched chain alkanes (up to 50%) and cycloalkanes, particularly in the upper end of the molecular weight distribution. Paraffin waxes contain alkanes up to approximately 600 molecular weight, whereas microcrystalline waxes can contain alkanes up to 1100 molecular weight. Today refinery crude oils tend to be purchased from a variety of sources, which leads to variations in the wax products from the lube stream. Also paraffin and microcrystalline waxes have a large range of uses, either singly or as blends, or blended with other polymers. Therefore there is a need to characterize the refinery waxes, blended waxes, and end-user products. The main problems in characterizing waxes arise from the solid nature of the material and the difficulty in separating the material into its components, particularly in the case of microcrystalline waxes. ASTM Test Method D4419, Measurement of Transition Temperatures of Petroleum Waxes by Differential Scanning Calorimetry, 2 was produced in 1984 as a more accurate means of evaluating the melt characteristics of a wax. In the 1980s, ASTM D02.04 developed a gas chromatographic method, originally intended for the analysis of wax blends used in the rubber industry'. However, by the time the method was published, in 1993, the scope of the method had changed to ASTM Test Method D5442, Analysis of Petroleum Waxes by Gas Chromatography. 2 More recent innovations in nuclear magnetic resonance (NMR) instrumentation for measuring the oil content of waxes has led to the possibility of an alternative test to replace the lengthy ASTM Test Methods D721, Oil Content of Petroleum Waxes, 2 and D3235, Solvent Extractables in Petroleum Waxes. 2

Gas Liquid Chromatography


The separation of waxes on packed columns has been carried out since the 1960s [2,3 ], and capillary column chromatography was used in 1970 to separate a microcrystalline wax up to carbon chain length (also known as carbon number) n-Csa [4]. In the early 1980s, tire manufacturers requested ASTM D02.04 to produce a capillary column gas chromatography method to analyze rubber waxes (with oil content of less than 10%) from carbon number n-C~7 to n-C44. ASTM D02.10, the Subcommittee on Petroleum Wax, was asked by D02.04 to carry out the development of the method. By the time ASTM D5442 was issued, the scope of the method had been changed to encompass all petroleumderived waxes, including blends of waxes, from n-C17 to n-C44 using an n-Cl~ internal standard. The sample is diluted in a suitable solvent (cyclohexane is suggested), containing the n-C~6 internal standard. It is then injected into a capillary column, meeting a specified resolution, and the components are detected using a flame ionization detector. The eluted components are identified by comparison to a standard mixture containing every fourth alkane from n-Ct6 to n-C44. The resulting chromatogram is complex, and the area of each straight chain and branched chain alkane must be measured using a programmable integrator or computer chromatography software. ASTM Method D5442 outlines a complex procedure for measuring the amount of each n-alkane and associated iso-alkanes, which is difficult to carry out in an accurate manner. Immediately after the issuance of D5442, it was realized that the Scope of the method (alkanes from n-CI 7 to n-C44) was applicable only to the analysis of paraffin waxes, exclud31

CURRENT PRACTICES
Analytical methods for waxes were originally based on physical tests, which are clearly explained in the ASTM Manual on Significance of Tests for Petroleum Products [1 ].1 Waxes are traded on the basis of the melting point range (e.g., 130 to 135F melting point) as defined by ASTM Test Methods D87, Melting Point of Petroleum Wax (Cooling Curve), 2 or D127, Drop Melting Point of Petroleum Wax Including Petrolatum. 2 The growth in the reliability of sophisticated instrumentation has coincided with the need by wax blenders and users for more detailed "fingerprinting" of materials to obtain more precise quality control and detailed information. ~The italic numbers in brackets refer to references at the end of this chapter. 2Appears in this publication.

32 MANUAL ON H Y D R O C A R B O N A N A L Y S I S
ing h i g h e r c a r b o n n u m b e r waxes. The availability of n-Cs0 a n d n-C60 s t a n d a r d s enables the m e t h o d to be extended to m i c r o c r y s t a l l i n e waxes. Also, the existing m e t h o d does not (1) take into account r e s e a r c h w o r k c a r r i e d out in the later p a r t of the 1980s on the effect of different integration methods that w o u l d result in i m p r o v e d a c c u r a c y of wax c h r o m a t o g r a p h y results a n d (2) include the use of p r o g r a m m a b l e t e m p e r a t u r e v a p o r i z e r (PTV) injectors [5,6]. The accurate quantitative analysis of microcrystalline waxes up to n-CT0 using the PTV injector was further amplified by Ludwig [7 ] in 1995 (30 years after his original p a p e r on w a x c h r o m a t o g r a p h y [3 ]). A review of the m e t h o d has t a k e n place, a n d it is h o p e d that a new r o u n d - r o b i n evaluation can be c a r r i e d out before the next revision of D5442 to validate (1) the use of the PTV injector, (2) use of the n-Cs0 a n d n-C60 standards, a n d (3) substitution of a new s i m p l e r calculation methodology. An N M R m e t h o d has n o w b e e n developed, in conjunction with Oxford I n s t r u m e n t s , as a suitable alternative to ASTM Methods D721 a n d D3235. The N M R m e t h o d provides a r a p i d d e t e r m i n a t i o n of oil content, a unified m e t h o d for all wax oil content/solvent extractables analysis (covering the r a n g e 0.2 to 35% oil content), the exclusion of hot solvents, a n d it is easy to analyze the oil c o n t e n t of microcrystalline waxes. The c a l i b r a t i o n for this m e t h o d can n o w be c o m p a r e d with the present ASTM D721 b y using the LGC3004, 0.54% oil in wax s t a n d a r d CRM. A p r o p o s e d draft ASTM m e t h o d is being written for circulation a m o n g i n s t r u m e n t m a n u f a c t u r ers a n d users. It is h o p e d that the final draft will be jointed with the Institute of P e t r o l e u m a n d other s t a n d a r d i z a t i o n bodies so that a n i n t e r n a t i o n a l r o u n d r o b i n test can be carried out with sufficient participants.

FUTURE TRENDS

Oil Content Analysis


During wax refining, increasing a m o u n t s of oil are removed, a n d this process needs to be controlled. Also, the oil content of slackwaxes, petrolatum, a n d waxes m u s t be assessed for end user specification. F o r high oil content waxes (i.e., greater t h a n 15%), ASTM Test M e t h o d D3235 was devised. This m e t h o d involves a lengthy p r o c e d u r e of dissolving a weighed a m o u n t of wax in a mixture of methyl ethyl ketone (MEK) a n d toluene, followed b y cooling to - 32C to precipitate the wax. The oil a n d solvent are removed; then the solvent is e v a p o r a t e d off to p r o d u c e a weighable a m o u n t of oil. GLC analysis of the solvent-extracted m a t e r i a l has shown that the d e t e r m i n e d "oil" contains a small a m o u n t of additional wax, Y/-CI7to r/-C22 alkanes, t h e r e b y p r o d u c i n g a small error. ASTM Test M e t h o d D721 was devised for waxes containing less t h a n 15% oil. It is used in the specification of food-contact a p p r o v e d waxes a n d for waxes used in explosives. This m e t h o d is similar to ASTM D3235, b u t uses only M E K as the solvent. Both m e t h o d s take over half a day to complete, are l a b o r intensive, p r o d u c e variable results, a n d c a n n o t easily be used to analyze the oil content of microcrystalline waxes. This is not very useful for refinery process control, n o r for the analysis of wax m a t e r i a l s used in food-contact applications, etc. Refineries have o v e r c o m e this lengthy p r o c e d u r e by using various n u c l e a r m a g n e t i c r e s o n a n c e (NMR) techniques, calib r a t e d using waxes analyzed by either ASTM D721 o r D3235. In 1997 the UK L a b o r a t o r y of the G o v e r n m e n t Chemist (LGC) p r o d u c e d a wax certified reference m a t e r i a l with an oil content of 0.54% (Reference CRM:LGC 3004) [8]. This is useful as a n analytical quality control s t a n d a r d a n d overcomes the p r o b l e m of i n t e r l a b o r a t o r y disputes. Over the p a s t three years there has been a growing interest in the use of pulse NMR for the analysis of waxes for oil content. This technique relies on the fact that, after a wax has experienced a pulse of r a d i o - f r e q u e n c y radiation, the signals received f r o m the solid a n d liquid phases decay at different rates a n d that the a m p l i t u d e of each signal is p r o p o r t i o n a l to each p h a s e present. The solid signal decays r a p i d l y whereas the liqu!d signal lasts m u c h longer. The s a m p l e is cooled so that the wax is totally solid a n d the liquid signal is p r o p o r tional to the oil content.

In the next five years the p r o b l e m s associated w i t h the GLC analysis of waxes should be resolved, a n d there should be a n e w ASTM m e t h o d using N M R to m e a s u r e the oil content/ solvent extractables. Also, ASTM Test Method D4419 needs to be u p d a t e d a n d e x p a n d e d to i n c o r p o r a t e the m e a s u r e m e n t of wax enthalpy so t h a t the degree of crystallinity can be estimated. There also needs to be i m p r o v e m e n t s to ASTM Test M e t h o d D1833, Test M e t h o d for O d o r of Petroleum Wax, a w h i c h requires at least five people examining the o d o r of a wax u n d e r rigorous conditions. It is not a very practical test for small, m o d e r n laboratories. Solvent odors can be quantified by h e a d s p a c e GLC, but o t h e r odors, such as those due to oxidation, are m o r e complex a n d difficult to detect. F o r several years the possibility has b e e n explored of using a new type of i n s t r u m e n t a t i o n that consists of up of 32 sensors acting as an "electronic nose" to analyze h e a d s p a c e emissions. The responses from the multi-elements of the detector are complex a n d variable. Therefore, the electronic signals m u s t be processed as a neural network, a n d each a r o m a has to be "learned" by the software. These i n s t r u m e n t s are capable of m e a s u r i n g odors from individual waxes b u t will need further d e v e l o p m e n t to be of practical use for analyzing a variety of waxes. This example illustrates that there is still plenty of scope for the d e v e l o p m e n t of new m e t h o d s for the analysis of h y d r o c a r b o n s in waxes.

REFERENCES
[1 ] Dyroff, G. V., Ed., Manual on Significance of Tests for Petroleum Products, Chap. 10, ASTM Manual Series MNL1, 6th ed., 1993. [2 ] Scott, C. G. and Rowel1, D. A., Nature, Vol. 187, 1960, p. 143. [3 ] Ludwig, F. J., Analytical Chemistry, Vol. 37, 1965, p. 1732. [4 ] Gouw, T. H., Whittemore, I. M., and Rentoft, R. E., Analytical Chemistry, Vol. 42, 1970, p. 1394. [5 ] Barker, A. D. in "Wax Chromatography--The 80's Crossroads," Petroanalysis '87, G. B. Crump, Ed., John Wiley & Sons Ltd., New York, 1988. [6 ] Barker, A. D., "The Chromatographic Analysis of Refined and Synthetic Waxes," Journal Chromatography Library, Vol. 56,

aAnnual Book of ASTM Standards, Vol. 05.01.

C H A P T E R 5 - - A N A L Y S I S OF W A X E S Chromatography in the Petroleum Indust~, E. R. Adlard, Ed.,


Elsevier Science B.V., New York, 1995. [7 ] Ludwig, Sr., F. J., Journal of Chromatography A., Vol. 718, 1995, p. 119.

33

[8 ] Petroleum Wax Oil Content CRM: Reference No. LGC 3004; Office of Reference Materials, Laboratory of the Government Chemist, Queens Road, Teddington, Middlesex, TW11 0LY, England.

Analysis of Crude Oils


by Axel J. Lubeck
INTRODUCTION
CRUDE OILS are a highly complex combination of hydrocarbons; heterocyclic compounds of nitrogen, oxygen, and sulfur; organometallic compounds; inorganic sediment; and water. Approximately 600 different hydrocarbons have been identified in crude oil, and it is likely that thousands of compounds occur, many of which probably will never be identified. In a study sponsored by the American Petroleum Institute (API), nearly 300 individual hydrocarbons were identified in Ponca City, Oklahoma crude oil [1,2 ].2 Some 200 individual sulfur compounds were identified in a 20-year systematic study of four crude oils [3 ]. Not only is the composition of crude oil highly complex, it is also highly variable from field-to-field, and even within a given field it is likely to exhibit inhomogeneity. Physical and chemical characterization of this complex mixture is further complicated for the analyst by the fact that crude oils are not pure solutions, but commonly include colloidally suspended components, dispersed solids, and emulsified water. Compared to refined products such as gasoline and aviation turbine fuel, there is relatively little in the literature on the analysis and characterization of crude oils. Indeed, for many years, there were relatively few ASTM methods specific to crude oils, although a number of ASTM methods had been adapted for use in analyzing crudes. This situation may have resulted, at least in part, from the historical tendency of refinery chemists to independently develop or modify analytical methods specific to their needs and subsequently for the methods to become company proprietary. In recent years, the unique problems associated with sampling and analysis of crude oils have received more attention, and more methods for determining selected constituents and characteristics of crude oils are now being standardized. A series of articles [4-9 ] illustrate the diversity of crude oil assay practices employed by major refiners in the United States and Austria. The dissimilarity of results reported in the literature [10 ] is a reflection of this independent development of analytical schemes, even though standardized approaches to crude oil analysis have previously been published [11,12 ]. Despite the complexity of crude oil composition and the diversity of analytical methodology, probably more crude oil analyses are routinely performed on a daily basis using inher~This chapter is an updated and modified version of the chapter, authored by H. N. Giles, found in the previous edition of this manual. 2The italic numbers in brackets refer to the list of references at the end of this chapter. 34

6
ently similar methods than are analyses on any single refined petroleum product except, possibly, gasoline. The overriding issue when performing comprehensive crude oil assays is economics. Crude oils are assayed to determine: (a) the slate of products that can be produced with a given refinery's process technology; (b) the processing difficulties that may arise as a result of inherent impurities; and (c) the downstream processing and upgrading that may be necessary to optimize yields of high-value, specification products. The analytical results are typically stored in an electronic database that can be accessed by computer models that generate refinery-specific economic valuations of each crude or crude slate (i.e., mixture of crudes processed together). Analyses are also performed to determine whether each batch of crude oil received at the refinery gate meets expectations. Does the crude receipt match the database assay so that the projected economic valuations and operational strategies are valid? Has any unintentional contamination or purposeful adulteration occurred during gathering, storage, or transport of the crude oil that may increase the processing cost or decrease the value of the refined products? The information needed to answer these questions is often refinery-specific--a function of the refinery's operating constraints and product slate. To obtain the desired information, two different analytical schemes are commonly used, namely, an inspection assay and a comprehensive assay. Inspection assays usually involve determination of a few key whole crude oil properties such as API gravity, sulfur content, and pour point--principally as a means of determining if major changes in a crude oil stream's characteristics have occurred since the last comprehensive assay was performed. Additional analyses may be performed to help ensure that the cargo or shipment received is that which is expected; to ascertain the quantity of impurities such as salt, sediment, and water; and to provide other critical refinery-specific information. Inspection assays are routinely performed on all shipments received at a refinery. The comprehensive assay, on the other hand, is complex, costly, and time-consuming and is normally performed only when a new field comes on stream, or when the inspection assay indicates that significant changes in the stream's composition have occurred. Except for these circumstances, a comprehensive assay of a particular crude oil stream may not be updated for several years.

CHAPTER 6 - - A N A L Y S I S OF CRUDE OILS

35

CURRENT PRACTICES Inspection Assays


Inspection assays comprise a limited number of tests generally restricted to the whole crude oil. Based on published data, there is little agreement as to what constitutes an inspection assay. As the data are primarily for intra-company use, there is little driving force for a standard scheme. At a bare minimum, API gravity and sulfur content are usually determined, although it is useful to also know the pour point, which provides some basic perception of the crude oil's aromaticity. A more detailed inspection assay might consist of the following tests: API gravity (or density or relative density), total sulfur content, pour point, viscosity, salt content, and water and sediment content. Individual refiners may substitute or add tests (e.g., trace metals or organic halides) that may be critical to their operations. Coupling the results from these few tests of a current crude oil batch with the archived data from a comprehensive assay, the process engineer will be able to estimate generally the product slate that the crude will yield and any extraordinary processing problems that may be encountered.

API Gravity
Accurate determination of the gravity of crude oil is necessary for the conversion of measured volumes to volumes at the standard temperature of 15.56C (60F) (ASTM D1250, Petroleum Measurement Tables). 3 Gravity is also a factor reflecting the quality of crude oils. API gravity is a special function of relative density (specific gravity) represented by the following: API gravity, deg -- (141.5/sp gr 60/60F) - 131.5 API gravity, or density or relative density, can be determined easily using one of two hydrometer methods [ASTM Test Method D287, API Gravity of Crude Petroleum and Petroleum Products (Hydrometer Method) 3 or ASTM Test Method D1298, Density, Relative Density (Specific Gravity) or API Gravity of Crude Petroleum and Liquid Petroleum Products by Hydrometer Method ].3 An instrumental method that is finding increasing popularity (ASTM Test Method D5002, Density and Relative Density of Crude Oils by Digital Density Analyzer)3 may also be used.

a sample in oxygen to convert the sulfur to sulfur dioxide, which is collected and subsequently titrated iodometrically or detected by non-dispersive infrared [ASTM Test Method D1552, Sulfur in Petroleum Products (High-Temperature Method) ].3 An even older method involving combustion in a bomb with subsequent gravimetric determination of sulfur as barium sulfate [ASTM Test Method D129, Sulfur in Petroleum Products (General Bomb Method)]4 is not as accurate as the high-temperature method, possibly because of interference from the sediment inherently present in crude oil. The older, classical techniques are being supplanted by two instrumental methods (ASTM Test Method D4294, Sulfur in Petroleum Products by Energy-Dispersive X-Ray Fluorescence Spectroscopy and ASTM Test Method D2622, Sulfur in Petroleum Products by X-Ray Spectrometry). 3 D4294 has slightly better repeatability and reproducibility than the hightemperature method and is adaptable to field applications; however, this method can be affected by some commonly present interferences such as halides. D2622 has even better precision and the capability of correcting for interferences, but is currently limited to laboratory use, and the equipment is more expensive. Hydrogen sulfide and mercaptans are commonly determined by non-aqueous potentiometric titration with silver nitrate [13 ].

Salt Content
The salt content of crude oil is highly variable and results principally from production practices used in the field and, to a lesser extent, from its handling aboard tankers bringing it to terminals. The bulk of the salt present will be dissolved in coexisting water and can be removed in desalters, but small amounts of salt may be dissolved in the crude oil itself. Salt may be derived from reservoir or formation waters, or from other waters used in secondary recovery operations. Aboard tankers, ballast water of varying salinity may also be a source of salt contamination. Salt in crude oil may be deleterious in several ways. Even in small concentrations, salts will accumulate in stills, heaters, and exchangers leading to fouling that requires expensive cleanup. More importantly, during flash vaporization of crude oil certain metallic salts can be hydrolyzed to hydrochloric acid according to the following reactions: 2NaC1 + H20--~ 2 HC1 + Na20

Sulfur Content
The sulfur content of a crude oil, which may vary from less than 0.1 to over 5 mass-%, is one of its most important quality attributes. Sulfur compounds contribute to corrosion of refinery equipment and poisoning of catalysts, cause corrosiveness in refined products, and contribute to environmental pollution as a result of the combustion of fuel products. Sulfur compounds may be present throughout the boiling range of crude oils although, as a rule, they are more abundant in the heavier fractions. In some crude oils, thermallylabile sulfur compounds can decompose on heating to produce hydrogen sulfide that is highly toxic and very corrosive. Until recently, one of the most widely used methods for determination of total sulfur content has been combustion of 3Appears in this publication.

MgC12 + H20--* 2 HCI + MgO The hydrochloric acid evolved is extremely corrosive, necessitating the injection of a basic compound, such as ammonia, into the overhead lines to minimize corrosion damage. Salts and evolved acids can also contaminate both overhead and residual products, and certain metallic salts can deactivate catalysts. A thorough discussion of the effects of salt on crude processing is included in a manual on impurities in petroleum [14 ]. The salt content is routinely determined by comparing the conductivity of a solution of crude oil in a polar solvent to that of a series of standard salt solutions in the same solvent [ASTM Test Method D3230, Salts in Crude Oil (Electrometric

4Annual Book of ASTM Standards, Vol. 05.01.

36

MANUAL ON H YD R O C A R B O N A N A LYSI S
ture divided by the specific gravity, at 60/60F. It has conveniently been related to viscosity and API gravity [16 ]. Typically, paraffin base crudes have K > 12.2, intermediate base crudes have K values of 11.4 to 12.2, and naphthene base crudes have K < 11.4 [17 ]. Pour point is determined by cooling a preheated sample at a specified rate and examining its flow characteristics at intervals of 3C (ASTM Test Method D5853, Pour Point of Crude Oils). 3 Viscosity is determined by measuring the time for a volume of liquid to flow under gravity through a calibrated glass capillary viscometer [ASTM Test Method D445, Kinematic Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity)]. 3 Tables are available for converting kinematic viscosity in centistokes at any temperature to Sayholt Universal viscosity in Sayhoh Universal seconds at the same temperature, and for converting kinematic viscosity in centistokes at 122 and 210F to Saybolt Furol viscosity in Saybolt Furol seconds at the same temperatures (ASTM Method D2161, Conversion of Kinematic Viscosity to Sayholt Universal Viscosity or to Saybolt Furol Viscosity). 4 By determining viscosity at two temperatures such as 25 and 37.78C, viscosity at any other temperature over a limited range may be interpolated or extrapolated using viscosity-temperature charts (ASTM D341, Viscosity-Temperature Charts for Liquid Petroleum Products). 3

Method)]. 3 It is necessary, however, to employ other methods, such as atomic absorption, inductively-coupled argon plasma spectrophotometry, and ion-chromatography to determine the composition of the salts present.

Water and Sediment


The water and sediment content of crude oil, like salt, results from production and transportation practices. Water, with its dissolved salts, may occur as easily removable suspended droplets or as an emulsion. The sediment dispersed in crude oil may be comprised of inorganic minerals from the production horizon or from drilling fluids, and scale and rust from pipelines and tanks used for oil transportation and storage. Usually water is present in far greater amounts than sediment but, collectively, it is unusual for them to exceed one percent of the crude oil on a delivered basis. Like salt, water and sediment can foul heaters, stills, and exchangers and can contribute to corrosion and to deleterious product quality. Also, water and sediment are principal components of the sludge that accumulates in storage tanks and must be disposed of periodically in an environmentally acceptable manner. Knowledge of the water and sediment content is also important in accurately determining net volumes of crude oil in sales, taxation, exchanges, and custody transfers. A number of methods exist for the determination of water and sediment in crude oil. Centrifugal separation of the water and sediment [ASTM Test Methods D96, Water and Sediment in Crude Oil by Centrifuge Method (Field Procedure) or D4007, Water and Sediment in Crude Oil by the Centrifuge Method (Laboratory Procedure)]a is rapid, relatively inexpensive, and adaptable to field conditions but, almost invariably, the amount of water detected is lower than the actual water content. A more accurate method for sediment entails extraction with hot toluene in a refractory thimble (ASTM Test Method D473, Sediment in Crude Oils and Fuels Oils by the Extraction Method).3 Improved techniques for measuring water content include heating under reflux conditions with a water immiscible solvent that distills as an azeotrope with the water (ASTM Test Method D4006, Water in Crude Oil by Distillation), 3 potentiometric titration (ASTM Test Method D4377, Water in Crude Oils by Potentiometric Karl Fischer Titration), 3 or the more generally preferred coulometric titration (ASTM Test Method D4928, Water in Crude Oils by Coulometric Karl Fischer Titration). 3 The latter two Karl Fischer methods include a homogenization step designed to re-disperse any water that has separated from the crude oil since the original sample was taken.

Trace Elements
A number of trace elements have been detected in crude oil but, aside from nickel and vanadium, which are usually the most abundant, relatively little systematic analytical work has been carried out. Over 30 trace metals are known to occur naturally in crude oils [l&19] and, with the increasing sophistication of analytical methodology, it is likely that other elements will be detected. Knowledge of the trace element constituents is important because they can have an adverse effect on petroleum refining and product quality. Elements such as iron, arsenic, and lead are catalyst poisons. Vanadium compounds can cause refractory damage in furnaces, and sodium compounds have been found to cause superficial fusion on fire bricks [20 ]. Some organometallic compounds are volatile, which can lead to contamination of distillate fractions [21 ] and a reduction in their stability or malfunctions of equipment when they are combusted. Concentration of the non-volatile organometallics in heavy products (e.g., premium coke) can have a significant impact on price, salability, and use. Several analytical methods are available for the routine determination of trace elements in crude oil, some of which allow direct aspiration of the samples (diluted in a solvent) instead of the time-consuming sample preparation procedures such as wet ashing (acid decomposition) or flame or dry ashing (removal of volatile/combustible constituents). Among the techniques used for trace element determinations are flameless and flame atomic absorption (AA) spectrophotometry (ASTM Test Method D5863, Determination of Nickel, Vanadium, Iron, and Sodium in Crude Oils and Residual Fuels by Flame Atomic Absorption Spectrometry) 3 and inductively-coupled argon plasma spectrophotometry [ASTM Test Method D5708, Determination of Nickel, Vanadium, and Iron in Crude Oils and Residual Fuels by Inductively-Coupled Plasma (ICP) Atomic Emission Spectrometry]. 3 ICP has an

Pour Point and Viscosity


Pour point and viscosity determinations of crude oils are performed principally to ascertain their handling characteristics at low temperatures. There are, however, some general relationships about crude oil composition that can be derived from pour point and viscosity data. Commonly, the lower the pour point of a crude oil the more aromatic it is, and the higher the pour point, the more paraffinic it is. There are numerous exceptions to this rule-of-thumb, and other data must be used to verify a crude oil's character. Probably the most widely used index is the Characterization or K Factor [15 ], which was originally defined as the cube root of the average molal boiling point in F absolute (Rankine) tempera-

CHAPTER 6--ANALYSIS OF CRUDE OILS


advantage over AA because it can determine a number of elements simultaneously, although detection limits by AA are often better. X-ray fluorescence spectrophotometry is also sometimes used, although matrix effects can be a problem. The method to be used is generally a matter of individual preference.

37

Comprehensive Assays
In addition to the whole crude oil tests performed as part of the inspection assay, a comprehensive or full assay requires that the crude be fractionally distilled and the fractions characterized by appropriate tests. This is necessary so that the refiner can assess the quantity and quality of products recoverable from a given crude oil and determine if that product slate economically satisfies the market requirements of a particular refinery. Refiners tailor a comprehensive assay to their individual needs, and the number of cuts or fractions taken may vary from as few as 4 to as many as 24. The following eight fractions will provide the basis for a moderately thorough evaluation: C2-C5 C5-79C 79-121C 121-191C 191-277C 277-343C 343-566C 566C + Gas Light naphtha Medium naphtha Heavy naphtha Kerosine Distillate fuel oil Gas oil or lube stock Residuum

Other Tests
Other properties that are determined on a more limited basis include the following:

Vapor Pressure--[ASTM Test Method D323, Vapor Pressure of Petroleum Products (Reid Method) or ASTM D5191, Vapor Pressure of Petroleum Products (Mini Method)]) Total Acid Number--to provide an indication of the naphthenic acids content (ASTM Test Method D664, Acid Number of Petroleum Products by Potentiometric Titration). 3 Carbon Residue--amount left after evaporation and pyrolysis to provide some indication of relative coke-forming propensity (ASTM Test Method D189, Conradson Carbon Residue of Petroleum Products, ASTM Test Method D524, Ramsbottom Carbon Residue of Petroleum Products, or ASTM Test Method D4530, Determination of Carbon Residue (Micro Method)), 3 ASTM Method D4530 having gained wide acceptance. Total Nitrogen Content--(ASTM Test Method D3228, Total Nitrogen in Lubricating Oils and Fuel Oils by Modified Kjeldahl Method), 5 (ASTM Test Method D4629, Trace Nitrogen in Liquid Petroleum Hydrocarbons by Syringe/ Inlet Oxidative Combustion and Chemiluminescence Detection, ASTM Test Method D5762, Nitrogen in Petroleum and Petroleum Products by Boat-Inlet Chemiluminescence)) Organic Chloride Content--by distillation and sodium biphenyl reduction or microcoulometry (ASTM Test Method D4929, Determination of Organic Chloride Content in Crude Oil). 3 Waxes and Asphaltenes--by solvent extraction; and determination of optical density color by spectrophotometrically measuring the absorbance of a solution of the crude oil in isooctane (2,2,4-trimethylpentane) or other suitable solvent. With increasing frequency, refinery engineers desire an estimate of the distillation yields of a crude oil. These can be provided rapidly, without the performance of a conventional pot distillation, using gas chromatography (ASTM Test Method D5307, Determination of the Boiling Range Distribution of Crude Petroleum by Gas Chromatography). 3 The inspection assay tests discussed above are undoubtedly not exhaustive, but are the ones most commonly used. These tests will provide the refiner with data on the impurities present and a general idea of the products that may be recoverable. However, they will not provide the data essential to determining whether a given crude oil or blend of crude oils will yield an economically attractive product slate. This requires that a comprehensive assay be performed.

SAnnual Book of ASTM Standards, Vol. 05.02.

Commonly, from five to 50 L of crude oil will be needed for a comprehensive assay, depending on the number of cuts to be taken and the tests to be performed on the fractions. Fractionation of the crude oil begins with a true boiling point (TBP) distillation employing a fractionating column having an efficiency of 14 to 18 theoretical plates and operated at a reflux ratio of 5 : 1 [ASTM Test Method D2892, Distillation of Crude Petroleum (15-Theoretical Plate Column)]) The TBP distillation may be used for all fractions up to a maximum cut point of about 350C atmospheric equivalent temperature (AET), provided reduced pressure is used to minimize cracking. Beyond an AET of 350C, it is necessary to continue the distillation at further reduced pressures under conditions that provide approximately a one-theoretical plate fractionation (ASTM Test Method D1160, Distillation of Petroleum Products at Reduced Pressure). 3 This fractionation may be continued up to a maximum liquid temperature of approximately 400C at a pressure of 0.13 kPa (1 mm Hg)(640C AET) provided significant cracking does not occur. In 1992 a new standard was published [ASTM Test Method D5236, Distillation of Heavy Hydrocarbon Mixtures (Vacuum Potstill Method)]3 that is seeing increasingly more use and appears to be supplanting D 1160 as the method of choice for crude assay vacuum distillations. Wiped-wall or thin-film molecular stills can also be used to separate the higher boiling fractions under conditions that minimize cracking. In these units, however, cut points cannot be directly selected, because vapor temperature in the distillation column cannot be measured accurately under operating conditions. Instead, the wall (film) temperature, pressure, and feed rate that will produce a cut equivalent to a D 1160 (or D5236) fraction with a given end point are determined from in-house correlations developed by matching yields between the wiped-wall distillation and the D1160 (or D5236) distillation. Despite the indirect approach, wiped-wall stills are often used because they allow higher end points than the D1160 or D5236 test methods and can easily provide large quantities of material for characterization.

38

MANUAL ON HYDROCARBON ANALYSIS Kerosine


Typically, density or specific gravity, total sulfur, mercaptan sulfur, hydrogen sulfide, aniline point (ASTM Test Method D611, Aniline Point and Mixed Aniline Point of Petroleum Products and Hydrocarbon Solvents), 3 total acid or neutralization number, naphthalenes content (ASTM Test Method D 1840, Naphthalene Hydrocarbons in Aviation Turbine Fuels by UV Spectrophotometry), 3 smoke point (ASTM Test Method D1322, Smoke Point of Aviation Turbine Fuels), 3 total nitrogen (see Note 1), viscosity, and freezing point (ASTM Test Method D2386, Freezing Point of Aviation Fuels) 3 would be determined for this fraction and a cetane index calculated (ASTM Test Method D976, Calculated Cetane Index of Distillate Fuels or ASTM Test Method D4737 for Calculated Cetane Index by Four Variable Equation). 3 Other tests that might be performed, depending on the intended end use of the fraction, are flash point (ASTM Test Method D56, Flash Point by Tag Closed Tester), 3 corrosiveness (ASTM Method D130, Detection of Copper Corrosion from Petroleum Products by the Copper Strip Tarnish Test), 3 and thermal stability [ASTM Test Method D3241, Thermal Oxidation Stability of Aviation Turbine Fuels (JFTOT Procedure)] .3

Following fractionation of the crude oil, each of the fractions is analyzed to determine one or more of its physical or chemical characteristics depending on the needs of the refiner. All of the various tests that could be performed on each of the fractions are too numerous to be included here. In the following discussion, the properties or constituents generally measured in a detailed analysis of each of the above eight fractions are listed.
Gas

Typically, the gas or debutanization fraction is analyzed by high-resolution gas chromatography for quantitative determination of individual C2 to C4 and total C5 hydrocarbons. Relative density (specific gravity) can be calculated from the compositional analysis.

Light Naphtha
Density or specific gravity by hydrometer or (ASTM Test Method D4052, Density and Relative Density of Liquids by Digital Density Meter), 3 total sulfur (ASTM Test Method D2622, ASTM Test Method D3120, Trace Quantities of Sulfur in Light Liquid Petroleum Hydrocarbons by Oxidative Microcoulometry, or ASTM Test Method D5453, Determination of Total Sulfur in Light Hydrocarbons, Motor Fuels, and Oils by Ultraviolet Fluorescence), 3 mercaptan sulfur [ASTM Test Method D3227, Mercaptan Sulfur in Gasoline, Kerosine, Aviation Turbine, and Distillate Fuels (Potentiometric Method)], 3 hydrogen sulfide, and organic chlorides are typically determined on this fraction. Because this fraction is important both as a petrochemical feedstock and as a gasoline blending component, it is likely that it would also be analyzed by high-resolution gas chromatography for quantitative determination of its paraffin, isoparaffin, aromatic, naphthene (cycloparaffin), and olefin, if any, components (PIANO analysis). Octane numbers would also be determined for this fraction if it were to be included as a gasoline blending component. Typically, octane numbers are determined using special engines that require relatively large volumes of sample (ASTM Test Method D2699, Knock Characteristics of Motor Fuels by the Research Methods and ASTM Test Method D2700, Knock Characteristics of Motor and Aviation Fuels by the Motor Method). 6 Some companies are now using semi-micro methods that require considerably less sample than the above standard methods for determination of octane numbers [22 ]. Other laboratories use PIANO data to calculate octane numbers [5 ].

Note 1--In general, the ratio of basic to total nitrogen is


practically constant at 0.3:1 for crude oils and virgin stocks. It also appears that the types of nitrogen compounds present in various crude oils are essentially the same, although the actual amounts may vary considerably [23 ]. Consequently, in most assays it is sufficient to determine total nitrogen (by the modified Kjeldahl or chemiluminescence methods).

Distillate Fuel Oil


Tests of the fuel oil fraction normally include determination of density or specific gravity, total sulfur, aniline point, total acid number, naphthalenes content, smoke point, total nitrogen, viscosity, cloud point (ASTM Test Method D2500, Cloud Point of Petroleum Oils), 3 pour point (ASTM Test Method D97, Pour Point of Petroleum Oils), 3 and calculation of cetane index. Corrosiveness, ash (ASTM Test Method D482, Ash from Petroleum Products), 3 and carbon residue might also be determined in more thorough evaluations.

Gas Oil and Lube Stocks


Density or specific gravity, total sulfur, aniline point, total nitrogen, viscosity, cloud point, pour point, trace metals (Fe, Ni, V), and carbon residue would normally be determined on this fraction. If the fraction is to be used as catalytic cracker feedstock, asphaltenes would also be determined by precipitation with normal-heptane (ASTM Test Method D3279, Heptane Insolubles). 3 Wax content determination by solvent reflux [24 ] might be included in a lube stock evaluation. Hydrocarbon-type analysis by mass spectrometry or other means is an important part of lube stock evaluation, but this is beyond the scope of this chapter.

Medium and Heavy Naphthas


Density or specific gravity, total sulfur, mercaptan sulfur, hydrogen sulfide, organic chloride, and PIANO determinations would normally be determined on these fractions. Included in the information that can be derived from the PIANO analysis are the concentrations of benzene and benzene precursors (compounds that ultimately form benzene in a refinery's reforming unit). These data are important because of governmental regulations limiting the maximum concentration of benzene in reformulated gasoline.
6Annual Book of ASTM Standards, Vol. 05.04.

Residuum
Tests of the residuum typically include density or specific gravity, total sulfur, total nitrogen, viscosity, trace metals, and carbon residue. Determination of the properties of asphalt such as penetration (ASTM Test Method D5, Penetra-

C H A P T E R 6 - - A N A L Y S I S OF C R U D E O I L S tion of Bituminous Materials), 3 softening point [ASTM Test Method D36, Softening Point of Bitumen (Ring-and-Ball Apparatus) ],3 and viscosity (ASTM Test Method D2171, Viscosity of Asphalts by Vacuum Capillary Viscometer or ASTM Test Method D3205, Viscosity of Asphalt with Cone and Plate Viscometer) 3 would also be included in some assays. However, new specifications for asphalt have been developed by the Strategic Highway Research Program (SHRP) and test methods are being standardized by the American Association of State Highway and Transportation Officials (AASHTO) and ASTM. These test methods will replace some of the existing asphalt test methods as states adopt the SHRP specifications. The tests listed for each fraction and for the whole crude oil assay are not exhaustive but are illustrative of those used to evaluate quality. A more thorough discussion [25 ] of the significance of many of the above tests, as well as methods for the assessment of product quality, is available. As noted earlier, refiners tailor their analytical scheme to their particular crude oil and product slates, although one refiner is reported to have said "The best crude oil assay is a 100,000 bbl run through my refinery" [26 ]. While this opinion carries some validity, the assay methods presented here provide quantity and quality data that are sufficient for most refiners to evaluate crude oil streams, and, in some instances, assay information is the ounce of prevention that precludes the need for a refinery to apply the pound of cure. With the proliferation of computer "assay" programs [9 ], many refiners no longer need to perform comprehensive assays as frequently as in the past. An inspection assay is all that is required for them to anticipate and plan for processing problems that will be caused by varying levels of impurities in the crude oil stream.

39

FUTURE TRENDS
The crude oils being processed in refineries are on average becoming increasingly heavier (more residuum) and more sour (higher sulfur content). To produce a viable product slate with these crudes, refiners must add to or expand existing treatment and processing options. The high sulfur content of crude coupled with government regulations limiting the maximum sulfur content of fuels makes sulfur removal a priority in refinery processing. In addition, refinery economics dictate that the "bottom of the barrel" (residuum) must be upgraded to higher value products. New treatment and process units in the refinery usually translate into a need for new analytical test methods that can adequately evaluate feedstocks and monitor product quality. Sulfur reduction processes are sensitive to both amount and structure of the sulfur compounds being removed. Tests that can provide information about both are becoming increasingly important. A number of laboratories have combined the separation power of gas chromatography with sulfur-selective detectors to provide data on the boiling range distribution of the sulfur compounds and probable molecular types, as well. A method (ASTM Test Method D5623, Sulfur Compounds in Light Petroleum Liquids by Gas Chromatography and Sulfur Selective Detection) 3 has been standardized for sulfur compounds in the gasoline boiling range. Work on extending this type of analysis to higher boiling ranges is on-

going. In addition, gas chromatography detectors that provide selectivity for other constituents of interest (e.g., nitrogen, organometallics) are also available and being used for characterization. Upgrading the "bottom of the barrel" involves taking more (ideally all) of the residuum and processing it into a more salable, higher valued product. Whatever the means to this end, improved characterization methods are necessary for process design, crude oil evaluation, and operational control. Among the characterization methods under development by industry, instrument vendor, and commercial laboratories are ones that define the boiling range and the hydrocarbontype distribution. Boiling range distribution of heavy distillates and residua are increasingly being carried out by hightemperature simulated distillation (HTSD) by gas chromatography. An HTSD test method applicable to distillates with end points up to 700C is currently in the balloting process as a proposed ASTM standard. A separate HTSD method is in use for residuum-containing materials, including crude oils [27 ]. This method provides a quantitative boiling range distribution (that accounts for non-eluting components) in a single analysis as opposed to two analyses required by D5307. However, the method has not yet been submitted to ASTM for standardization. The distributions of hydrocarbon types in gas oil and heavier materials are important in evaluating them as feedstocks for further processing. Some ASTM member laboratories are working to update older mass spectrometric methods for determining hydrocarbon types (ASTM Test Method D3239, Aromatic Types Analysis of Gas-Oil Aromatic Fractions by High Ionizing Voltage Mass Spectrometry and ASTM Test Method D2786, Hydrocarbon Types Analysis of Gas Oil Saturates Fractions by High Ionizing Voltage Mass Spectrometry) 3 for use with modern quadrupole mass spectrometers, either with batch inlets or with gas chromatographic inlets (GC/MS). Another technique that has been successfully applied for determining hydrocarbon types in these materials involves use of high-performance liquid chromatography [28]. Providing comparable information to the mass spectrometric methods, the HPLC method is yet to be submitted to ASTM for standardization. From the examples above, it is obvious that automated, instrumental analyses continue to be the option of choice when developing new methods. There is no indication that this propensity will wane. The primary motivation for this trend, if anything, is increasing. Labs are continually seeking to reduce analysis time (especially analyst's time) and improve the quality of test results (in these cases by eliminating dependency on the manual skills of the analyst). Fueled by rapid advances in technology, more of the same is expected as the analytical challenges of the industry are met.

REFERENCES
[l ] Rossini, F. D.. "Hydrocarbons in Petroleum," Journal of Chemical Education, Vol. 37, 1960, pp. 554-561. [2 ] Mair, B. J., "Annual Report for the Year Ending, June 30, 1967," American Petroleum Institute Research Project 6" Pittsburgh, PA, Carnegie Institute of Technology, 1967. [3 ] Rail, H.T., Thompson, C.J., Coleman, H.J., and Hopkins, R. L., "Sulfur Compounds in Oil," Bulletin 659, U.S. Department of the Interior, Bureau of Mines, 1972.

40

MANUAL ON HYDROCARBON

ANALYSIS [17] Nelson, W. L., "Which Base of Crude Oil is Best?" The Oil and Gas Journal, Jan. 8, 1979, pp. 112-113. [18 ] Valkovi6, V., Trace Elements in Petroleum, The Petroleum Publishing Co., Tulsa, OK, 1978. [19 ] Yen, T. F., Ed., The Role of Trace Metals in Petroleum, Ann Arbor Science Publishers, Inc., Ann Arbor, MI, 1975. [20 ] Jones, M. C. K. and Hardy, R. L., "Petroleum Ash Components and Their Effect on Refractories," Industrial and Engineering Chemistry, Vol. 44, 1952, pp. 2615-2619. [21 ] Woodle, R. A. and Chandler, W. B., Jr., "Mechanisms of Occurrence of Metals in Petroleum Distillates," Industrial and Engineering Chemistry, Vol. 44, 1952, pp. 2591-2596. [22 ] Childs, W. V. and Vickery, E. H., "The Phillips Small Sample Octane Number Methods, Automation of a Knock-Test Engine," Symposium on Laboratory and Pilot Plant Automation, Washington, DC, August 28-September 2, 1983, American Chemical Society, Washington, DC, 1983, pp. 979-990. [23 ] Richter, F.P., Caesar, P.D., Meisel, S.L., and Offenhauer, R. D., "Distribution of Nitrogen in Petroleum According to Basicity," Industrial and Engineering Chemistry, Vol. 44, 1952, pp. 2601-2605. [24] Asphaltene Precipitation with Normal Heptane, IP 143/84, Standard Methods for Analysis and Testing of Petroleum and Related Products, Vol. 1, Institute of Petroleum, London, 1988. [25 ] Dyroff, George V., Ed., Manual on Significance of Tests for Petroleum Products, 6th ed., American Society for Testing and Materials, West Conshohocken, PA, 1993. [26 ] Aalund, L. R., "Guide to Export Crudes for the '80s-- 1," The Oil and Gas Journal, April 1, 1983, p. 71. [27 ] Villalanti, D. C., Janson, D., and Colle, P., "Hydrocarbon Characterization by High Temperature Simulated Distillation," Session 4, AIChE Spring Meeting, Houston, TX, March 19-23, 1995. [28 ] Application Note 9701, "Characterization of Vacuum Gas Oils by the AC Heavy Distillates Analyzer," AC--Analytical Controls Inc., Bensalem, PA.

[4 ] Csoklich, Ch., Ebner, B., and Schenz, R., "Modern Crude Oil Practices-Austria's OEMV," The Oil and Gas Journal, March 21, 1983, pp. 86-90. [5 ] O'Donnell, R. J., "Modern Crude Oil Practices--Standard Oil of California Companies," The Oil and Gas Journal, pp. 90-93. [6 ] McNelis, F. B., "Modern Crude Oil Practices--Exxon Organizations," The Oil and Gas Journal, pp. 94-97. [7 ] Wampler, R. J. and Kirk, E. L., "Modern Crude Oil Practices-Gulf Companies," The Oil and Gas Journal, pp. 98-104. [8 ] Nelson, G.V., Schierberg, G. R., and Sequeira, A., "Modern Crude Oil Practices--The Texaco System," The Oil and Gas Journal, pp. 108, 112, 116, 118-120. [9 ] McCleskey, G. and Joffe, B. L., "Modern Crude Oil Practices-Phillips Petroleum Co.," The Oil and Gas Journal, pp. 124, 126-127. [10] Aalund, L. R., "Guide to Export Crudes for the '80s--1 to 13," The Oil and Gas Journal, April 11, May 2, 23, June 6, 20, July 4, 25, Aug. 22, Sept. 5, Oct. 24, Nov. 7, 21, Dec. 12, 19, 1983. [11 ] O'Donnell, J., "Crude Oils," Criteria for Quality of Petroleum Products, J. P. Allison, Ed., John Wiley, New York, 1973, pp. 10-21. [12 ] Smith, N. A. C., Smith, H. M., Blade, O. C., and Garton, E. L., "The Bureau of Mines Routine Method for the Analysis of Crude Petroleum 1. The Analytical Method," Bulletin 490, U.S. Department of the Interior, Bureau of Mines, 1951. [13 ] Hydrogen Sulfide and Mercaptan Sulfur in Liquid Hydrocarbons by Potentiometric Titration, Method 163, UOP Laboratory Test Methods for Petroleum and Its Products, UOP Inc., Des Plaines, IL, 1989. [14 ] Impurities in Petroleum, Petrolite Corporation, Houston, 1958. [15 ] Watson, K. M., Nelson, E. F., and Murphy, G. B., "Characterization of Petroleum Fractions," Industrial and Engineering Chemistry, Vol. 27, 1935, pp. 1460-1464. [16 ] Calculation of UOP Characterization Factor and Estimation of Molecular Weight of Petroleum Oils, Method 375, UOP Laboratory Test Methods for Petroleum and Its Products, UOP Inc., Des Plaines, IL, 1986.

Analysis of Aromatic Hydrocarbons


by Charles H. Pfeiffer
INTRODUCTION
THE HISTORYOF INDUSTRIALanalyses of aromatic hydrocarbons began in the 1920s when the production of benzene from coke by-products became commercially viable. By the 1930s, the rapid growth in demand for benzene as well as the commercial production of heavier aromatics led to the formulation of a considerable number of empirical analytical procedures. At this time, ASTM Committee D16 on Aromatic Hydrocarbons was formed. In the more than 50 years that this group has been active, the changes in analytical techniques have progressed hand-in-hand with the advancements in process technology and the expansion in the demand for high-purity aromatic products. As coal was heated in the absence of oxygen to produce coke, the lighter chemicals were vaporized and separated from the coal. Cooling the vapors condensed a highly aromatic liquid. Fractional distillation was used to separate the hydrocarbons into narrow-boiling fractions representing single aromatics, such as benzene, or groups of aromatics, such as xylenes. The contaminants were largely sulfur-, oxygen-, and nitrogen-containing hydrocarbons. Estimates of the purity of these products were determined in laboratories using procedures such as ASTM Test Methods D850, Distillation of Industrial Aromatic Hydrocarbons and Related Materials, 1 and D852, Solidification Point of Benzene. t Contaminants in the products caused corrosion and product degradation in the downstream units. The following ASTM Test Methods were developed to address these problems: ASTM Test Methods D853, Hydrogen Sulfide and Sulfur Dioxide Content (Qualitative) of Industrial Aromatic Hydrocarbons/ D848, Acid Wash Color of Industrial Aromatic H y d r o c a r b o n s / a n d D849, Copper Strip Corrosion of Industrial Aromatic Hydrocarbons. ~ As processes improved, aromatic hydrocarbons became available at substantially higher purities. The higher product purities opened up new industrial applications and required new standards. To make these materials easier to buy, sell, and trade, ASTM Test Methods D1015, Freezing Points of High-Purity Hydrocarbons,2 D 1016, Purity of Hydrocarbons from Freezing Points, 2 and D 1078, Distillation Range of Volatile Organic Liquids/ were published. Later, methods that gave more specific compositional information would supplant these empirical tests. 1Appears in this publication.
2Annual Book of ASTM Standards, Vol. 05.01.

7
Eventually all of the light aromatics obtainable from the coking operation were being used and shortages occurred. The world needed another source, and that source was petroleum. Even as early as the late 1920s, crude oil was evaluated as a source of light aromatics. Not until the late 1940s, however, did the development of catalytic reforming and liquidliquid extraction provide large quantities of aromatic hydrocarbons for use by the chemical industry and as a blending ingredient in high-octane gasoline.

CURRENT PRACTICES
Cyclohexane, made from benzene, is a chemical intermediate in the production of nylon. Polyester is made from p-xylene, which is extracted from mixed xylenes. Synthetic rubber is made from styrene, which is made from ethylbenzene. Resins are made from phenol, which is made from cumene. Each of these feedstocks and intermediates requires a specific purity level as well as limits on specific impurities and groups of impurities. ASTM test methods were developed and revised in ASTM Committee D16 as each of these needs were identified and as requirements for each of the materials changed. Gas chromatography (GC) has become a primary technique for determining hydrocarbon impurities in individual aromatic hydrocarbons and the composition of mixed aromatic hydrocarbons. Although a measure of purity by GC is often sufficient, GC is not capable of measuring absolute purity; not all possible impurities will pass through the GC column, and not all those that do will be measured by the detector. Absolute purity is best measured by distillation range or freeze or solidification points. Despite this caveat, GC is a standard, widely used technique and is the basis of many current ASTM Committee D16 test methods for aromatic hydrocarbons. Most of these methods, listed below, were written with, or converted to, fused silica capillary columns. D2306 D2360 D3054 D3760 D3797 41 Cs Aromatic Hydrocarbon Analysis by Gas Chromatography ~ Trace Impurities in Monocyclic Aromatic Hydrocarbons by Gas Chromatography 1 Purity and Benzene Content of Cyclohexane by Gas Chromatography I Analysis of Isopropylbenzene (Cumene) by Gas Chromatography ~ Analysis of o-Xylene by Gas Chromatography ~

42

MANUAL ON HYDROCARBON ANALYSIS Analysis of p-Xylene by Gas Chromatography ~ Analysis of Benzene by Gas Chromatography 1 Benzene Content of Cyclic Products by Gas Chromatography 1 Determination of Trace Thiophene in Refined Benzene by Gas Chromatography ~ Determining Impurities in High-Purity Ethylbenzene by Gas Chromatography ~ Analysis of Styrene by Capillary Gas Chromatography 1 Analysis of High Purity Benzene for Cyclohexane Feedstock by Capillary Gas Chromatography 1 Trace Impurities in Monocyclic Aromatic Hydrocarbons by Gas Chromatography and External Calibration 1 Analysis of AMS (a-Methylstyrene) by Gas Chromatography I D1493 D1555 D1686 Solidification Point of Industrial Organic Chemicals 4 Calculation of Volume and Weight of Industrial Aromatic Hydrocarbons4 Color of Solid Aromatic Hydrocarbons and Related Materials in the Molten State (Platinum-Cobalt Scale) 4 Aldehydes in Styrene Monomer 4 Polymer Content of Styrene Monomer 4 Peroxides in Styrene Monomer 4 Apparent Density of Industrial Aromatic Hydrocarbons 4 Phenol Content of Cumene (Isopropylbenzene) or AMS (~-Methylstyrene) 4 Density or Relative Density of Pure Liquid Chemicals 4 Purity of Styrene by Freezing Point Method 4 Colorimetric Determination of p-tert-Butylcatechol in Styrene Monomer or AMS (a-Methylstyrene) by Spectrophotometry4

D3798 D4492 D4534 D4735 D5060 D5135 D5713 D5917

D2119 D2121 D2340 D2935 D3160 D3505 D3799 D4590

D6144

When classes of hydrocarbons, such as olefins, need to be measured, techniques such as bromine index are used. ASTM Test Method D1492, Bromine Index of Aromatic Hydrocarbons by Coulometric Titration/ continues as a useful method, but D1491, Bromine Index of Aromatic Hydrocarbons by Potentiometric Titration, 3 was withdrawn in 1985 because of health concerns regarding its use of carbon tetrachloride as a solvent. It was eventually replaced by D5776, Bromine Index of Aromatic Hydrocarbons by Electrometric Titration,~ which is based on D2710, Bromine Index of Petroleum Hydrocarbons by Electrometric Titration, ~but uses the less toxic 1-methyl-2-pyrrolidinone as a solvent. Impurities other than hydrocarbons are of concern in the petroleum industry. For example, many catalytic processes are sensitive to sulfur contaminants. Consequently, ASTM committees responded by developing a series of state-of-theart methods to determine trace concentrations of sulfur-containing compounds. These methods included ASTM Test Methods D 1685, Traces of Thiophene in Benzene by Spectrophotometry/D3961, Trace Quantities of Sulfur in Liquid Aromatic Hydrocarbons by Oxidative Microcoulometry, D4045, Sulfur in Petroleum Products by Hydrogenolysis and Rateometric Colorimetry, 1 and D4735, Trace Thiophene in Refined Benzene by Gas ChromatographyJ Chloride-containing impurities are determined by ASTM Test Methods D5194, Trace Chloride in Liquid Aromatic Hydrocarbons/ and D5808, Determining Organic Chloride in Aromatic Hydrocarbons and Related Chemicals by Microcoulometry. l Nitrogen-containing impurities are determined by ASTM Test Method D6069, Trace Nitrogen in Aromatic Hydrocarbons by Oxidative Combustion and Reduced Pressure Chemiluminescence DetectionJ Many of these test methods have sensitivity to 1 mg/kg, reflecting the needs of industry to determine very low levels of these contaminants. In addition to those tests previously mentioned, a number of other ASTM Test Methods are regularly used for the analysis of aromatics and are listed below: D847 Acidity of Benzene, Toluene, Xylenes, Solvent Naphthas, and Similar Industrial Aromatic Hydrocarbons 4

FUTURE TRENDS
Timeliness of analyses and the amount of labor required to perform them continue to grow in importance. Although many laboratories have limits on staffing, they may still be able to make a one-time capital purchase of equipment to make the available staff more productive. Instrumental and automated methods are replacing chemical and physical methods in the laboratories, and ASTM is supporting this trend by writing test methods using contemporary technology and by listing these test methods in ASTM specifications. The ability of ASTM Committee D16 to write these methods in a timely manner has been made possible, in part, by increased vendor activity, a trend that is expected to continue. For relative density, most labs now use ASTM Test Method D4052, Density and Relative Density of Liquids by Digital Density Meter. 1 Distillation methods have been or are being rewritten to include automated distillation apparatus. For trace sulfur, D4045 has become the industry standard. Recently, this method has been optimized for aromatics analysis as ASTM Test Method D6212, Total Sulfur in Aromatic Compounds by Hydrogenolysis and Rateometric ColorimetryJ Development in D16.0E on a proposed method, "Total Sulfur in Aromatic Compounds by Oxyhydropyrolysis and Difference Photometry," is continuing, utilizing new equipment. Methods for trace sulfur and trace nitrogen by electrochemical detection have also been proposed. The classic platinum-cobalt color method, ASTM Test Method D1209, Color of Clear Liquids (Platinum-Cobalt Scale)/which requires subjective visual color comparison, is slowly being replaced by methods such as ASTM Test Method D5386, Color of Liquids Using Tristimulus Colorimetry.l This new standard is currently limited to a maximum color of 30 because, for higher color values, the vendors' algorithms to convert tristimulus values to Pt-Co color produce different results. Currently, three major instrument manufacturers are 4Annual Book of ASTM Standards, Vo]. 06.04.

3Discontinued; see 1985 Annual Book of ASTM Standards, Vol. 06.03.

CHAPTER 7 - - A N A L Y S I S OF AROMATIC HYDROCARBONS


working together on a common algorithm, which may be published as an appendix to the standard. The labor requirements of GC methods are also being addressed. Traditionally, trace analyses by GC have been quantitated using an internal standard for calibration. These test methods require careful weighing procedures for each sample. Now, with the routine use of autosamplers to provide repeatable injections, an external standard procedure is preferred as a means of saving analyst time. Trace impurities by GC, ASTM Test Method D5917, was written as an equivalent to the internal standard GC method D2360. Because of continuing concerns over labor requirements, ASTM Committee D 16 is currently trying to eliminate redundant tests in Committee DI6 Specifications. For example, if a specification for high-purity benzene includes distillation range, purity by GC, and solidification point, a density or

43

relative density test is not justified. Similarly, current commercial high-purity aromatic hydrocarbons always pass acidity, copper corrosion, hydrogen sulfide, and sulfur dioxide tests, so the continuing need for these tests on a routine basis is being questioned. More stringent product requirements, advanced catalytic processing techniques, improved feedstock purification for specific downstream processes, and health and environmental requirements are driving the limits of impurities into the less than parts-per-million range. Efforts to provide quantitative analyses at this level continue. As raw material sources, product distributions, and methodologies change, efforts to publish methods based on current technology will continue to go hand-in-hand with these industrial technological changes.

Part 2--ASTM Test Methods


The test m e t h o d s herein are a r r a n g e d in a l p h a n u m e r i c sequence. The page n u m b e r s a p p l y only to this m a n u a l a n d not to the s t a n d a r d d o c u m e n t s as they a p p e a r in the a n n u a l ASTM Book of Standards. See Table 2 in the front of this m a n u a l for a list of test m e t h o d s b y subject.

45

l]~ Designation:

5 - 95

Standard Test Method for Penetration of Bituminous Materials I


This standard is issued under the fixed de~gnation D 5; the number immediately following the de~gnation indicates the year of original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A superscript epsilon (E) indicates an editorial change since the last revision or reapproval.

This test method has been approved for use by agencies of the Department of Defense. Consult the DoD Index of Specifications and Standards for the specific year of issue which has been adopted by the Department of Defense.

1. Scope 1. I This test method covers determination of the penetration of semi-solid and solid bituminous materials. 1.2 The needles, containers and other conditions described in this test method provide for the determinations of penetrations up to 500. 1.3 The values stated in SI units are to be considered standard. 1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

5. Significance and Use 5.1 The penetration test is used as a measure of consistency. Higher values of penetration indicate softer consistency. 6. Apparatus 6.1 Penetration ApparatusDAny apparatus that permits the needle holder (spindle) to move vertically without measurable friction and is capable of indicating the depth of penetration to the nearest 0.1 ram, will be acceptable. The weight of the spindle shall be 47.5 + 0.05 g. The total weight of the needle and spindle assembly shall be 50.0 + 0.05 g. Weights of 50 + 0.05 g and 100 0.05 g shall also be provided for total loads of I00 g and 200 g, as required for some conditions of the test.The surface on which the sample container rests shall be flatand the axis of the plunger shall be at approximately 90" to this surface. The spindle shall be easily detached for checking its weight. 6.2 Penetration Needle: 6.2.1 The needle (see Fig. 1) shall be made from fully hardened and tempered stainless steel, Grade 440-C or equal, HRC 54 to 60. The standard needle shall be approximately 50 mm (2 in.) in length, the long needle approximately 60 mm (24 in.). 6 The diameter of all needles shall be 1.00 to 1.02 mm (0.0394 to 0.0402 in.). It shall be symmetrically tapered at one end by grinding to a cone having an angle between 8.7 and 9.7" over the entire cone length. The cone should be coaxial with the straight body of the needle. The total axial variation of the intersection between the conical and straight surfaces shall not be in excess of 0.2 mm (0.008 in.). The truncated tip of the cone shall be within the diameter limits of 0.14 and 0.16 mm (0.0055 and 0.0063 in.) and square to the needle axis within 2". The entire edge of the truncated surface at the tip shall be sharp and free of burrs. When the surface texture is measured in accordance with American National Standard B46.1 the surface roughness height of the tapered cone shall be 0.2 to 0.3 ~tm (8 to 12 ~tin.) arithmetic average. The needle shall be mounted in a non-corroding metal ferrule. The ferrule shall be 3.2 0.05 mm (0.12 0.003 in.) in diameter and 38 1 mm (1.50 0.04 in.) in length. The exposed length of the standard nee~e shall be within the limits of 40 to 45 mm (1.57 to 1.77 in.), and the exposed length of the long needle shall be 50 to 55 mm (1.97 to 2.19 in.). The needle shall be rigidly mounted in the ferrule. The run-out (total-indicator reading) of the needle tip and any portion of the needle relative to the
e Long needles are available from Stanhope-Seta, Park Close, Englefleld Green, Eglmm, Surrey, U.K. TW20 OXD.

2. Referenced Documents 2.1 A S T M Standards: C 670 Practice for Preparing Precision and Bias Statements for Test Methods for Construction Materials2 D 36 Test Method for Softening Point of Bitumen (Ringand-Ball Apparatus) 3 E 1 Specification for ASTM Thermometers4 E 77 Test Method for Inspection and Verification of Liquid-in-Glass Thermometers4 2.2 ANSI Standard? B 46.1 Surface Texture
3. Terminology 3.1 Definition: 3.1.1 penetration, n--consistency of a bituminous material expressed as the distance in tenths of a millimeter that a standard needle vertically penetrates a sample of the material under known conditions of loading, time, and temperature.

4. Summary of Test Method 4.1 The sample is melted and cooled under controlled conditions. The penetration is measured with a penetrometer by means of which a standard needle is applied to the sample under specificconditions.
i This test method is under the jurisdiction of ASTM Committee D-4 on Road
and Paving Materials and is the direct responsibility of Subcommittee 1304.44 on

Rheolngical Tests. Current edition approved Sept. 10, 1995. Published February 1996. Originally published as D 5 - 59 T. Last previous edition D 5 - 94. 2 Annual Book of ASTM Standards, Vol 04.02. 3 Annual Book of ASTM Standards, Vol 04.04. 4 Annual Book of ASTM Standards, Vol 14.03. 5 Available from American National Standards Institute, I I W. 42nd St., 13th Floor, New York, NY 10036.

47

~ DS
,100 /o /02mm 0./4/o 0./6 m m d~4-O to 9dO '.- . '

e
.........
FiG. 1

"'r _1 approx. lL as required----L~-J~--"-'-"-~--'~=~----"

6.7 Thermometers--Calibrated liquid-in-glass thermometers of suitable range with subdivisions and maximum scale error of 0. I*C (0.2*F) or any other thermometric device of equal accuracy, precision and sensitivity shall be used. Thermometers shall conform to the requirements of Specification E 1. 6.7.1 Suitable thermometers commonly used are:
ASTM Number
17C or 17F Range 19 to 27*(2 (66 to 80F)

Needle for Penetration Test

ferrule axis shall not exceed 1 mm (0.04 in.). The weight of the ferrule needle assembly shall be 2.50 _.+ 0.05 g. (A drill hole at the end of the ferrule or a fiat on the side is permissible to control the weight.) Individual identification markings shall be placed on the ferrule of each needle; the same markings shall not be repeated by a manufacturer within a 3-year period. 6.2.2 Needles used in testing materials for conformance to specifications shall be shown to have met the requirements of 6.2.1 when tested by a qualified agency. 6.3 Sample ContainerV--A metal or glass cylindrical, fiat-bottom container of essentially the following dimensions shall be used:
For penetrations below 200:

63C or 63F 64(2 or 64F

- 8 to +32"(2 (18 to 89"F) 25 to 55"C (77 to 131"F')

6.7.2 The thermometer used for the water bath shall periodically be calibrated in accordance with Test Method E77.

Diameter, mm Internal depth, mm For penetrations between 200 and 350: Diameter, mm Internal depth, mm

55 35 55 70

6.4 Water B a t h - - A bath having a capacity of at least 10 L and capable of maintaining a temperature of 25 + 0. I*C or any other temperature of test within 0. I*C. The bath shall have a perforated shelf supported in a position not less than 50 mm from the bottom and not less than 100 mm below the liquid level in the bath. If penetration tests are to be made in the bath itself, an additional shelf strong enough to support the penetrometer shall be provided. Brine may be used in the bath for determinations at low temperatures.
NoTE l - - T h e use o f distilled water is recommended for the bath. Take care to avoid contamination o f the bath water by surface active agents, release agents, or other chemicals; as their presence may affect the penetration values obtained.

7. Preparation of Test Specimen 7.1 Heat the sample with care, stirring when possible to prevent local overheating, until it has become sufficiently fluid to pour. In no ease should the temperature be raised to more than 60"C above the expected softening point for tar pitch in accordance with Test Method D 36, or to more than 90"C above it for petroleum asphalt (bitumen). Do not heat samples for more than 30 min. Avoid incorporating bubbles into the sample. 7.2 Pour the sample into the sample container to a depth such that, when cooled to the temperature of test, the depth of the sample is at least 10 mm greater than the depth to which the needle is expected to penetrate. Pour two separate portions for each variation in test conditions. 7.3 Loosely cover each container as a protection against dust (a convenient way of doing this is by covering with a lipped beaker) and allow to cool in air at a temperature between 15 and 30"C for 1 to 1.5 h for the small container and 1.5 to 2 h for the taller. Then place the two samples together with the transfer dish, if used, in the water bath maintained at the prescribed temperature of test. Allow the smaller container to remain for 1 to 1.5 h and the taller (6 oz) container to remain for 1.5 to 2 h. 8. Test Conditions 8.1 Where the conditions of test are not specifically mentioned, the temperature, load, and time are understood to be 25"C (77"F), 100 g, and 5 s, respectively. Other conditions may be used for special testing, such as the following:
Temperature, "C ('F) 0 (32) 4 (39.2) 45 (113) 46.1 (I 15) Load, g 200 200 50 50 Time, s 60 60 5 5

6.5 Transfer D i s h - - W h e n used, the transfer dish shall have a capacity of at least 350 mL and of sufficient depth of water to cover the large sample container. It shall be provided with some means for obtaining a firm bearing and preventing rocking of the container. A three-legged stand with three-point contact for the sample container is a convenient way of ensuring this. 6.6 Timing Device--For hand-operated-penetrometers any convenient timing device such as an electric timer, a stop watch, or other spring activated device may be used provided it is graduated in 0.1 s or less and is accurate to within +0.1 s for a 60-s interval. An audible seconds counter adjusted to provide 1 beat each 0.5 s may also be used. The time for a 1 l-count interval must be 5 + 0.1 s. Any automatic timing device attached to a penetrometer must be accurately calibrated to provide the desired test interval within +0.1 s.
vSample Containers are available from Ellisco Inc., 6301 Eastern Ave., Baltimore MD, 21224 and Freund Can Co., 155 West 84th St., Chicago IL, 60620-1298.

In such cases the specific conditions of test shall be reported. 9. Procedure 9. I Examine the needle holder and guide to establish the absence of water and other extraneous materials. If the penetration is expected to exceed 350 use a long needle, otherwise use a short needle. Clean a penetration needle with toluene or other suitable solvent, dry with a clean cloth, and insert the needle into the penetrometer. Unless otherwise specified place the 50-g weight above the needle, making the total weight 100 + 0.1 g.

48

(I~Ti~ D S

9.2 If tests are to be made with the penetrometer in the bath, place the sample container directly on the submerged stand of the penetrometer (Note 2). Keep the sample container completely covered with water in the bath. If the tests are to be made with the penetrometer outside the bath, place the sample container in the transfer dish, cover the container completely with water from the constant temperature bath and place the transfer dish on the stand of the penetrometer. NOTE 2--For referee tests, penetrationsat temperatures other than 25C (77"F) should be made without removing the sample from the bath. 9.3 Position the needle by slowly lowering it until its tip just makes contact with the surface of the sample. This is accomplished by bringing the actual needle tip into contact with its image reflected on the surface of the sample from a properly placed source of fight (Note 3). Either note the reading of the penetrometer dial or bring the pointer to zero. Quickly release the needle holder for the specified period of time and adjust the instrument to measure the distance penetrated in tenths of a millimetre. If the container moves, ignore the result.
NOTE 3--The positioning of the needle can be materially aided by

TABLE 1

Precision Cr~llrli Standard Deviation or Coefficient of Variation (Is) or Acceptable Range of Two Test Results

Matedal

(is x) Single-operator predsion: Asphalts at 77"F (25*(3) below 50 0.35


1.1 5.2 1.4 2.8 1.4

(d2s) or (d2s ~)
1 3 15

penetration,units
Asphalts at 77"F (25"C) 50 penetration lull above, percent of thelr mean Tar pltct~s at 770F (250C)A percent of thelr mean

MulBaboratoryprec~~:
Asphalts at 770F (250C) below 50 penetration, units Asphalts at 770F (2SoC) 50 penetration and above, percent of thelr rnean Tar pitches at 770F (25*C),A units

,~ ~ N of predsk~ for tar pltches are _~___,~'J results from 2 pitches with on penetraUonof 7 and 24. Estimates may not be appUcal~ to apprec/ablyharder or softer matsdm.

using an illuminatedpoly-methylmethacrylatetube. 9.4 Make at least three determinations at points on the surface of the sample not less than 10 mm from the side of the container and not less than 10 mm apart. If the transfer dish is used, return the sample and transfer dish to the constant temperature bath between determinations. Use a clean needle for each determination. If the penetration is greater than 200, use at least three needles leaving them in the sample until the three determinations have been completed. 10. Report 10.1 Report to nearest whole unit the average of three penetrations whose values do not differ by more than the following:
0to 50to 150to

precision at other temperatures is being determined. 11.1.1 Single Operator PrecisionmThe single operator coefficient of variation has been found to be 1.4 % for penetrations above 60, and the single operator standard deviation has been found to be 0.35 % for penetrations below 50. Therefore, the results of two properly conducted tests by the same operator on the same material of any penetration, using the same equipment, should not differ from each other by more than 4 % of their mean, or I unit, whichever is larger. 11.1.2 Multilaboratory Precision--The multilaboratory coefficient of variation has been found to be 3.8 % for penetrations above 60, and the multilaboratory standard deviation has been found to be 1.4 for penetrations below 50. Therefore, the results of two properly conducted tests on the same material of any penetration, in two different laboratories, should not differ from each other by more than 11% of their mean, or 4 units, whichever is larger.
NOTE 4---These values represent, respectively, the dls (or dls %) and

250to
500

Penetration Maximum difference between highest and lowest penetration

49 2

149 4

249 12

20

11. Precision and Bias 11.1 Use the following criteria for judging the acceptability of penetration results for asphalt at 25"C. The

d2s (or d2s %) limits as d__~cri_ in PracticeC 670. "bed 11.1.3 Bias--This test method has no bias because the values determined arc defined only in terms of the test method. 12. Keywords 12.1 asphalt; bitumen; penetration

The American Society for Testing and Materials takes no position respecting the vahdity of any patent rights asserted in connection with any item mentioned in this standard. Users of this standard are expressly advised that determination of the vahdity of any such patent rights, and the risk of infringement of such rights, are entirely their own responsibility. This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards and should be addressed to ASTM Headquarters. Your comments will receive careful consideration at a meeting ol the responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should make your views known to the ASTM Committee on Standards, 100 Barr Herbor Drive, West Conshohocken, PA 19428.

49

(~~ll~ Designation: D 36 - 95
Standard Test Method for Softening Point of Bitumen (Ring-and-Ball Apparatus) 1
This standard is issued under the fixed designation D 36; the number immediately following the designation indicates the year of original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A superscript epsilon (~) indicates an editorial change since the last revision or reapproval.

1. Scope 1.1 This test method covers the determination of the softening point of bitumen in the range from 30 to 157"C (86 to 315"F) using the ring-and-ball apparatus immersed in distilled water (30 to 80"C), USP glycerin (above 80 to 157"C), or ethylene glycol (30 to 110*C). 1.2 The values stated in SI units are to be regarded as the standard. 1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

bitumens, as one element in establishing the uniformity of shipments or sources of supply, and is indicative of the tendency of the material to flow at elevated temperatures encountered in service.

2. Referenced Documents

2.1 ASTM Standards." C 670 Practice for Preparing Precision and Bias Statements for Test Methods for Construction Materials 2 D 92 Test Method for Flash and Fire Points by Cleveland Open Cup 3 D 140 Practice for Sampling Bituminous Materials4 D 3461 Test Method for Softening Point of Asphalt and Pitch (Mettler Cup-and-Ball Method) s E 1 Specification for ASTM Thermometers 6
3. Summary of Test Method 3.1 Two horizontal disks of bitumen, cast in shouldered brass rings, are heated at a controlled rate in a liquid bath while each supports a steel ball. The softening point is reported as the mean of the temperatures at which the two disks soften enough to allow each ball, enveloped in bitumen, to fall a distance of 25 mm (1.0 in.). 4. Significance and Use 4.1 Bitumens are viscoelastic materials without sharply defined melting points; they gradually become softer and less viscous as the temperature rises. For this reason, softening points must be determined by an arbitrary and closely defined method if results are to be reproducible. 4.2 The softening point is useful in the classification of
This test method is under the jurisdhction of ASTM Committee D-8 on Roofing, Waterproofing, and Bituminous Materials and is the direct responsibdity of Subcommittee I:)08.03 on Surfacing and Bituminous Materials for Membrane Waterproofing and Builtup Roofing. Current edition approved Oct. 10, 1995. Published December 1995. Originally published as D 36 - 62T. Last previous edition D 36 - 86 (1993) ~j. 2 Annual Book fASTM Standards, Vol 04.02. 3 Annual Book fASTM Standards, Vol 05.01. 4 Annual Book of ASTM Standards, Vol 04.03. 5 Annual Book of ASTM Standards, Vol 04.04. 6 Annual Book of ASTM Standards, Vol 14.03.

5. Apparatus 5.1 Rings--Two square-shouldered brass rings conforming to the dimensions shown in Fig. l(a). 5.2 Pouring Plate--A fiat, smooth, brass plate approximately 50 by 75 mm (2 by 3 in.). 5.3 Balls--Two steel balls, 9.5 mm (3/8 in.) in diameter, each having a mass of 3.50 _ 0.05 g. 5.4 Ball-Centering Guides--Two brass guides for centering the steel balls, one for each ring, conforming to the general shape and dimensions shown in Fig. 1 (b). 5.5 Bath--A glass vessel, capable of being heated, not less than 85 mm in inside diameter and not less than 120 mm in depth from the bottom of the flare.
NOTe I - - A n 800-mL, low-form Griffin beaker of heat-resistant glass meets this requirement.

5.6 Ring Holder and Assembly--A brass holder designed to support the two rings in a horizontal position, conforming to the shape and dimensions shown in Fig. 1 (c), supported in the assembly illustrated in Fig, 1 (d). The bottom of the shouldered rings in the ring holder shall be 25 mm (I.0 in.) above the upper surface of the bottom plate, and the lower surface of the bottom plate shall be 16 + 3 mm (% _+ I/s in.) from the bottom of the bath. 5.7 Thermometers: 5.7.1 An ASTM Low Softening Point Thermometer, having a range from - 2 to + 80"C or 30 to 180*F, and conforming to the requirements for Thermometer 15C or 15F as prescribed in Specification E 1. 5.7.2 An ASTM High Softening Point Thermometer, having a range from 30 to 200"C or 85 to 392"F, and conforming to the requirements for Thermometer 16C or 16F as prescribed in Specification E 1. 5.7.3 The appropriate thermometer shall be suspended in the assembly as shown in Fig. I (d) so that the bottom of the bulb is level with the bottom of the rings and within 13 mm (0.5 in.) of the rings, but not touching them or the ring holder. Substitution of other thermometers shall not be permittted.

6. Reagents and Materials 6.1 Bath Liquids: 6.1.1 Freshly Boiled Distilled Water.
NOTE 2 - - T h e use o f freshly boiled distilled water is essential to avoid trapping air bubbles on the surface o f the specimen which m a y affect the

results.

50

I1~ D 36

Q
-z3.o

.. - "1 ZO~
ss

"%~
iI i

Note: This diomefer to be

, / ~ slightly (opprox/motely O.OJ mmll /l. _.~ Iorger Ihon 9 ~ m m to o/Iowploc/n~:'~;-'~ ond centerin~ 9.5-ram steel boll.

i~qo. ~ , ~
"... -J

, ,

]0o
'

.-Rounded lrillef

I---,.

q.

_L
Note: diometer to be ~" full lg.0mm t o ~ r m # I n s e r t i o n ,, s of
I

P,'-- 15.9- ~1 --19.0- - ~

(o) Shouldered Ring I . "

Th/s ring.

l.-- ..o--J
Inside "D/ometer Full 23.0ram to slide over ring

(b) Boll Centering Guide

-4 s.61,~ , vIA r/~ rtld

rid

1/
'

ra

(c) Ring Holder

(d) Two-Ring Assembly NOTE~AIIdimensionsare in millimetres. FIG. 1 Shouldered Ring, Bali-Centering Guide, Ring Holder, and Assembly of Apparatus Showing Two Rings
6.1.2

USPGlycerin, or EthyleneGlycol,

in other tests such as those for penetration and flash point.

NOTE 3--CAUTION:--Glycerin has a flash point of 160"C (320"F) in accordance with Test Method D 92. 6.1.3 with a boiling point between 195 and 197"C (383 and 387"F). NOTE 4--CAUTION:--Ethylene glycol is toxic when taken internally or inhaled as a vapor. Avoid prolonged or repeated skin contact and inhalation of vapors. Its flash point is 115C (239F) in accordance with Test Method D 92. When using this bath liquid, conduct the test in a vented laboratory hood with adequate exhaust fan capacity to ensure removal of toxic vapors. 6.2 6.2.1 To prevent adhesion of bitumen to the pouring plate when casting disks, the surface of the brass pouring plate may be thinly coated just before use with silicone oil or grease (Note 5), a mixture o f glycerin and dextrin, talc, or china clay. NOTE 5--CAUTION:--Isolate silicones from other bituminous testing equipment and samples to avoid contamination, and wear disposable rubber gloves whenever handling silicones or apparatus coated with them. Silicone contamination can produce erroneous results 51

7. Sampling
7.1 Sample the material in accordance with Practice D 140. 8. Test

Specimens

Release Agenls."

8.1 Do not start unless it is planned to complete preparation and testing o f all asphalt specimens within 6 h and all coal-tar pitch specimens within 41/2 h. Heat the bitumen sample with care, stirring frequently to prevent local overheating, until it has become sufficiently fluid to pour (Note 6). Stir carefully to avoid incorporation of air bubbles in the sample. NOTE 6--An electric hot plate having a minimum power to unitsurface-area ratio of 37 k W / m 2 has been found satisfactory for this purpose. 8. I. l Take no more than 2 h to heat an asphalt sample to its pouring temperature; in no case shall this be more than 110*C (200*F) above the expected softening point o f the asphalt.

~
8.1.2 Take no more than 30 min to heat a coal-tar pitch sample to its pouring temperature; in no case shall this be more than 55"C (100*F) above the expected softening point of the coal-tar-pitch. 8.1.3 If the test must be repeated later, do not reheat this sample; use a fresh sample in a clean container to prepare new test specimens. 8.2 Heat the two brass rings (but not the pouring plate) to the approximate pouring temperature, and place them on the pouring plate treated with one of the release agents. 8.3 Pour a slight excess of the heated bitumen into each ring, and then allow the specimens to cool in ambient air for at least 30 min. For materials that are soft at room temperature, cool the specimens for at least 30 min at an air temperature at least 10*C (18*F) below the expected softening point. From the time the specimen disks are poured, no more than 240 min shall elapse before completion of the test. 8.4 When the specimens have cooled, cut away the excess bitumen cleanly with a slightly heated knife or spatula, so that each disk is flush and level with the top of its ring. 9. Procedure 9.1 Select one of the following bath liquids and thermometers appropriate for the expected softening point: 9.1.1 Freshly boiled distilled water for softening points between 30 and 80"C (86 and 176"F); use Thermometer 15C or 15F. The starting bath temperature shall be 5 +I*C (41 + 2*F). 9.1.2 U S P glycerin for softening points above 80"C (176"F) and up to 157"C (315"F); use Thermometer 16C or 16F. The starting bath temperature shall be 30 + I*C (86 2*F). 9.1.3 Ethylene glycol for softening points between 30 and 110C (86 and 230F); use Thermometer 16C or 16F. The starting bath temperature shall be 5 IC (41 2*F). 9.1.4 For referee purposes, all softening points up to 80*C (176F) shall be determined in a water bath and all softening points above 80C (176F) shall be determined in a glycerin bath. 9.2 Assemble the apparatus in the laboratory hood with the specimen rings, ball-centering guides, and thermometer in position, and fill the bath so that the liquid depth will be 105 3 mm (4'/8, '/s in.) with the apparatus in place. If using ethylene glycol, make sure the hood exhaust fan is turned on and operating properly to remove toxic vapors. Using forceps, place the two steel balls in the bottom of the bath so they will reach the same starting temperature as the rest of the assembly. 9.3 Place the bath in ice water, if necessary, or gently heat to establish and maintain the proper starting bath temperature for 15 min with the apparatus in place. Take care not to contaminate the bath liquid. 9.4 Again using forceps, place a ball from the bottom of the bath in each ball-centering guide. 9.5 Heat the bath from below so that the temperature indicated by the thermometer rises at a uniform rate of 5"C (9*F)/min (Note 7). Protect the bath from drafts, using shields if necessary. Do not average the rate of temperature rise over the test period. The maximum permissible variation for any l-rain period after the first 3 rain shall be 0.5"C

D 36
(_ 1.0*F). Reject any test in which the rate of temperature rise does not fall within these limits. NOTE 7--Rigid adherence to the prescribed heating rate is essential to reproducibility of results. Either a gas burner or electric heater may be used, but the latter must be of the low-lag, variable output type to maintain the prescribed rate of heating. 9.6 Record for each ring and ball the temperature indicated by the thermometer at the instant the bitumen surrounding the ball touches the bottom plate. Make no correction for the emergent stem of the thermometer. If the difference between the two temperatures exceeds I*C (2*F), repeat the test. 10. Calculation 10.1 For a given bitumen specimen, the softening point determined in a water bath will be lower than that determined in a glycerin bath. Since the softening point determination is necessarily arbitrary, this difference matters only for softening points slightly above 80"C (176*F). 10.2 The change from water to glycerin for softening points above 80"C creates a discontinuity. With rounding, the lowest possible asphalt softening point reported in glycerin is 84.5"C (184"F), and the lowest possible coal-tar pitch softening point reported in glycerin is 82.0"C (180*F). Softening points in glycerin lower than these translate to softening points in water of 80"C (176"F) or less, and shall be so reported. 10.2. l The correction for asphalt is -4.2"C (-7.6"F), and for coal-tar pitch is -1.7*C (-3.0*F). For referee purposes, repeat the test in a water bath. 10.2.2 Under any circumstances, if the mean of the two temperatures determined in glycerin is 80.0"C (176.0*F) or lower for asphalt, or 77.5"C (171.5*F) or lower for coal-tar pitch, repeat the test in a water bath. 10.3 To convert softening points slightly above 80"C (176"F) determined in water to those determined in glycerin, the correction for asphalt is +4.2"C (+7.6"F) and for coal-tar pitch is + 1.7*C (+3.0*F). For referee purposes, repeat the test in a glycerin bath. 10.3.1 Under any circumstances, if the mean of the two temperatures determined in water is 85.0"C (185.0"F) or higher, repeat the test in a glycerin bath. 10.4 Results obtained by using an ethylene glycol bath will vary from those using water and glycerin. The following formulas shall be used to calculate the differences:

Asphalt:
SP (glycerin) -- 1.026583 SP (ethylene glycol) - 1.334968C SP (water) = 0.974118 x SP (ethylene glycol) - 1.44459C

Coal Tar."
SP (glycerin) = 1.044795 x SP (ethylene glycol) - 5.063574C fSP (water) = 1.061111 x SP (ethylene glycol) - 8.413488C 11. Report 11.1 When using ASTM Thermometer 15C or 15F, report to the nearest 0.2"C or 0.5*F the mean or corrected mean of the temperatures recorded in 9.6 as the softening point. ? Editorially corrected. 52

o a6
11.2 When using ASTM Thermometer 16C or 16F report to the nearest 0.5"C or 1.0*F the mean or corrected mean of the temperatures recorded in 9.6 as the softening point. 11.3 Report the bath liquid used in the test. 12. Precision and Bias 12.1 With distilled water or USP glycerin, the following criteria shall be used for judging the acceptability of results (95 % probability): 12.1.1 Single-Operator Precision--The single-operator standard deviation has been found to be 0.41C (0.73F). Therefore, results of two properly conducted tests by the same operator on the same sample of bitumen should not differ by more than 1.2C (2.0F). 7 12.1.2 Multilaboratory Precision--The multilaboratory standard deviation has been found to be 0.70C (1.26F). Therefore, results of two properly conducted tests on the
These numbers represent, respectively, the (IS) and (D2S) limits as described in Practice C 670.

same sample of bitumen from two laboratories should not differ by more than 2.0"C (3.5"17).7 12.2 With ethylene glycol, the following criteria shall be used for judging the acceptability of results: 12.2. l Single-Operator Precision--The single-operator standard deviation has been found to be 0.72"C (1.29"F). Therefore, results of two properly conducted tests by the same operator on the same sample of bitumen should not differ by more than 2.0"C (3.5"F). 7 12.2.2 Multilaboratory Precision--The multilaboratory standard deviation has been found to be 1.08*C (1.95"F). Therefore, results of two properly conducted tests on the same sample of bitumen from two laboratories should not differ by more than 3.0"C (5.5"F). 7 12.3 BiasmThe procedure in Test Method D 36 has no bias because the value of the softening point of the bitumen test is defined in terms of this test method. 13. Keywords 13.1 asphalt; ball and ring; bitumen; coal tar; softening point

The American Society for Testing and Materials takes no position respecting the validity of any patent rights asserted in connechon with any item mentioned in this standard. Users o! this standard are expressly advised that determination of the validity of any such patent rights, and the risk of infringement of such rights, are entirely their own responsibility. This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and if not revised, either reapproved or withdrawn, Your comments are invited either for revision of this standard or for additional standards and should be addressed to ASTM Headquarters. Your comments will receive careful consideration at a meebng of the responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should make your views known to the ASTM Committee on Standards, 100 Barr Harbor Drive, West Conshohocken, PA 19428.

53

( ~ , ) Designation:D 56 - 97a
Standard Test Method for Flash Point by Tag Closed Tester 1
This standard is issued under the fixed designation D 56; the number immediately following the designation indicates the year of original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last renpproval. A superscript epsilon (e) indicates an editorial f~han~since the last revision or reapprovai.

This test method ha~ been approvedfor use by agencies of the Department of Defense. Consult the DoD Index of SpecOqcations and Standards for the specific year of issue which has been adopted by the Department of Defense. This test method has been adoptedfor use by gowrnment agencies to replaceMethod 1101 of Federal Test Method Standard No. 791b, and Method 4291 of Federal Test Method Standard No. 141A.
INTRODUCTION

To ensure an acceptable precision, this dynamic flash point test employs a prescribed rate o f temperature rise for the material under test. The rate of heating may not in all cases give the precision quoted in the test method because of the low thermal conductivity o f certain materials. To improve the prediction of flammability, Test Method D 3941, which utiliT~s a slower heating rate, was developed. Test Method D 3941 provides conditions closer to equilibrium where the vapor above the liquid and the liquid are at about the same temperature. If a specification requires Test Method D 56, do not change to D 3941 or other test method without permission from the specifier. 1. Scope 1.1 This test method covers the determination of the Flash Point, by Tag manual and automated closed testers, of liquids with a viscosity below 5.5 mm2/s (cSt) at 40C (104F), or below 9.5 mm2/s (cSt) at 25"C (77F), and a flash point below 93C (200"F). 1.1.1 For the closed-cup flash point of liquids with the following properties: a viscosity of 5.5 mm2/s (cSt) or more at 40C (104"1=); a viscosity o f 9.5 mm2/s (cSt) or more at 25C (77F); a flash point o f 93C (200F) or higher; a tendency to form a surface film under test conditions; or containing suspended solids, Test Method D 93 can be used. 1.1.2 For cut-back asphalts refer to Test Methods D 1310 and D 3143. NOTE l--The U.S. Department of Transportation (RSTA)2 and U.S. Department of Labor (OSHA) have established that liquids with a flash point under 37.8"C (100"F) are flammable as determined by this test method for those liquidswhich have a viscosityless than 5.5 mm2/s (cSt) at 40"C (104"F) or 9.5 mm2/s (cSt) or less at 25"C (77F), or do not contain suspended solids or do not have a tendency to form a surface film while under test. Other flash point classifications have been established by these departments for liquids using this test. 1.2 This standard can be used to measure and describe the properties o f materials, products, or assemblies in response to heat and flame under controlled laboratory conditions
i This test method is under the joint jurisdiction of ASTM Committee D-2 on Petroleum Products and Lubricants and is the direct responsibility of Subcommince 1302.08 on Volatility. Current edition approved May 10, 1997 and July 10, 1997. Published October 1997. Originally published as D 56 - 18 T. Last previous edition D 56 - 96. 2 For information on United States Department of Transportation regulations, see Codes of United States Regulation 49 CFR Chapter ! and for information on United States Department of Labor regulations, see Code of United States Regulation 29 CFR Chapter XVIL Each of these items are revised annually and may be procured from the Superintendent of Documents, Government Printing Office, Washington, DC 20402.

and cannot be used to describe or appraise the fire hazard or fire risk o f materials, products, or assemblies under actual fire conditions. However, results of this test can be used as elements of fire risk assessment which takes into account all of the factors which are pertinent to an assessment of the fire hazard of a particular end use. 1.3 Related Standards are Test Methods D 93, D 1310, D 3828, D 3278, and D 3941. 1.4 The values stated in SI units are to be regarded as standard. The values in parentheses are for information only. 1.5 This standard does not purport to address all of the

safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific
hazard statements see Note 4 and refer to Material Data Sheets.
2. R e f e r e n c e d D o c u m e n t s

Safety

2.1 A S T M Standards:
D93 Test Methods for Flash Point by Pensky-Martens Closed Cup Tester3 D 850 Test Method for Distillation of Industrial Aromatic Hydrocarbons and Related Materials4 D 1015 Test Method for Freezing Points of High-Purity Hydrocarbons3 D 1078 Test Method for Distillation Range of Volatile Organic Liquids4 D 1310 Test Method for Flash Point and Fire Points of Liquids by Tag Open-Cup Apparatus 5
s Annual Book of ASTM Standards, Vol 05.01. 4 Annual Book of ASTM Standards, Vo106.04. s Annual Book of ASTM Standards, Vo106.01.

54

~[~ D 5e
D 3143 Test Method for Flash Point of Cutback Asphalt with Tag Open-Cup Apparatus 6 D 3278 Test Methods for Flash Point of Liquids by Small Scale Closed Cup Apparatus 5 D3798 Test Method for Analysis of p-Xylene by Gas Chromatography 4 D3828 Test Methods for Flash Point by Small Scale Closed Tester7 D3941 Test Method for Flash Point by the Equilibrium Method with a Closed-Cup Apparatus s D4057 Practice for Manual Sampling for Petroleum and Petroleum Products 7 E 1 Specification for ASTM Thermometers s 2.2 Federal Test Method Standards: Method 1101, Federal Test Method Standard No. 791b 9 Method 4291, Federal Test Method Standard No. 141A9 2.3 ISO Standards: Guide 34 Quality Systems Guidelines for the Production of Reference Materials Guide 35 Certification of Reference Materials--General and Statistical Principles

4. Summary of Test Method 4.1 The specimen is placed in the cup of the tester and, with the lid closed, heated at a slow constant rate. An ignition source is directed into the cup at regular intervals. The flash point is taken as the lowest temperature at which application of the ignition source causes the vapor above the specimen to ignite. 5. Significance and Use 5.1 Flash point measures the tendency of the specimen to form a flammable mixture with air under controlled laboratory conditions. It is only one of a number of properties that must be considered in assessing the overall flammability ha,nrd of a material. 5.2 Flash point is used in shipping and safety regulations to define flammable and combustible materials. One should consult the particular regulation involved for precise definitions of these classes. 5.3 Flash point can indicate the possible presence of highly volatile and flammable materials in a relatively nonvolatile or nonflammable material. For example, an abnormally low flash point on a sample of kerosene can indicate gasoline contamination.
6. Sampling 6.1 Erroneously high flash points will be obtained when precautions are not taken to avoid the loss of volatile material. Containers should not be opened unnecessarily, to prevent loss of volatile material and possible introduction of moisture. Transfers should not be made unless the sample temperature is at least 10"C (18"F) below the expected flash point. When possible, flash point must be the first test performed on a sample and the sample must be stored at low temperature. 6.2 Samples are not to be stored in plastic (polyethylene, polypropylene, etc.) bottles, since volatile materials may diffuse through the walls of the bottle. Samples in leaky containers are suspect and not a source of valid results and shall be discarded in accordance with local regulations for flammable materials. 6.3 At least 50 mL of sample is required for each test. Refer to sampling Practice D 4057.

3. Terminology 3.1 Definition: 3.1.1 flash point--the lowest temperature corrected to a pressure of 101.3 kPa (760 mm Hg) at which application of an ignition source causes the vapors of a specimen of the sample to ignite under specified conditions of test. 3.1.1.1 Discussion--The specimen is deemed to have flashed when a flame appears and instantaneously propagates itself over the entire surface of the fluid. 3.1.1.2 Discussion--When the ignition source is a test flame, the application of the test flame may cause a blue halo or an enlarged flame prior to the actual flash point. This is not a flash and should be ignored. 3.2 Definitions of Terms Specific to This Standard: 3.2.1 dynamic (non-equilibrium)--in this type of flash point apparatus, the condition of the vapor above the specimen and the specimen are not at the same temperature at the time that the ignition source is applied. 3.2.1.1 Discussion--This is primarily caused by the heating of the specimen at the constant prescribed rate with the vapor temperature ]a~,~rtg behind the specimen temperature. The resultant flash point temperature is generally within the reproducibility of the method. 3.2.2 equilibrium--in that type of flash point apparatus or test method, the vapor above the specimen and the specimen are at the ~ m e temperature at the time the ignition source is applied. 3.2.2.1 Discussion--This condition may not be fully achieved in practice, since the temperature is not uniform throughout the specimen and the test cover and shutter is generally cooler.
e Annua/Book ofASTM .,~nnd~'ds, Vol 04.03. ' Annua/Book o f A S T M , S ~ , Vo105.02. s Annua/Book fASTM,S~andards, Vol 14.03. 9 Available from Supez~tendent of Document& U.S. Government Printing Office, Wmlfington, DC 20402. ,o Available from American National Standard11n~itute, II W. 42nd St., 13th Floor, New York, NY 10036.

7. Apparatus (Manual Instrument) 7.I Tag Closed Tester--The apparatus is shown in Fig. I and described in detailin Annex A I. 7.2 Shield--A shield460 m m (18 in.)square and 610 m m (24 in.)high, open in front,is recommended. 7.3 Thermometers--For the test cup thermometer, use one as prescribed in Table 1. For the bath thermometer, any convenient type that has an adequately open scale covering the required range may be used; it is often convenient to use the same type of thermometer as used in the test cup.
NOTE 2--Whenever thermomete~ complying with ASTM require. ments ate not available, thermometers complying with the requirements for The Institute of Petroleum thermometer IP 15C PM-Low can be

used.

8. Preparation of Apparatus (Manual) 8.1 Support the tester on a level steady table. Unless tests are made in a draft-free room or compartment, surround the tester on three sides by the shield for protection from drafts.
55

(~

D 56
by carefully lubricating the slide shutter with high-vacuum silicone lubricant.

Cup Thermometer Flame Size Bead

Both Thermometer

FlameTip / O=1 Chamber

Test Cup

Both

Bath Stand for Gas Burner

8.4 Verify the performance of the manual apparatus at least once per year by determining the flash point of a certified reference material (CRM), such as those listed in Annex A2, which is reasonably close to the expected temperature range of the samples to be tested. The material shall be tested according to the procedure of this test method and the observed flash point obtained in 9.5 shall be corrected for barometric pressure (see Section 13). The flash point obtained shall be within the limits stated in Table A2.1 for the identified CRM or within the limits calculated for an unlisted CRM (see Annex A.2). 8.5 Once the performance of the apparatus has been verified, the flash point of secondary working standards (SWSs) can be determined along with their control limits. These secondary materials can then be utilized for more frequent performance checks (see Annex A2). 8.6 When the flash point obtained is not within the limits stated in 8.4 or 8.5, check the condition and operation of the apparatus to ensure conformity with the details listed in Annex A1, especially with regard to tightness of the lid (A1.1.2), the action of the shutter, the position of the ignition source (AI. 1.2.3), and the angle and position of the temperature measuring device (A1.1.2.4). After any adjustment, repeat the test in 8.4 or 8.5 using fresh test specimen, with special attention to the procedural details prescribed in the test method. 9. Procedure (Manual) 9.1 Using a graduated cylinder and taking care to avoid wetting the cup above the final fiquid level, measure 50 :t: 0.5 mL of the sample into the cup, both the sample and graduated cylinder being precooled, when necessary, so that the specimen temperature at the time of measurement will be 27 + 5"C (80 + 10"F) or at least 10"C (18F) below the expected flash point, whichever is lower. It is essential that the sample temperature be maintained at least 10"C (18F) below the expected flash point during the transfers from the sample container to the cylinder and from the cylinder to the test cup. Destroy air bubbles on the surface of the specimens by use of knife point or other suitable device. Wipe the inside of the cover with a clean cloth or absorbent tissue paper; then attach the cover, with the thermometer in place, to the bath collar. 9.2 Light the test flame, when used, adjusting it to the size of the small bead on the cover. Operate the mechanism on the cover in such a manner as to introduce the ignition source into the vapor space of the cup, and immediately bring it up again. The time consumed for the full operation should be 1 s, allowing equal time periods for the introduction and return. Avoid any hesitation in the operation of depressing and raising the ignition source. When a flash is observed on the initial operation of the mechanism, discontinue the test and discard the result. In this case, a fresh sample shall be cooled an additional 10C (18"F), below the original specimen installation temperature. 9.2.1 Care must be exercised when using a test flame, if the flame is extinguished it cannot ignite the specimen and the gas entering the vapor space can influence the result. When the flame is prematurely extinguished the test must be 56

I~
,

Gas Burner

RG. 1 Tag ClosedFluh Tester(Ihnuell


Tests are not to be made in a laboratory draft hood or near ventilators. 8.2 Natural gas and bottled gas flame and electric ignitors have been found acceptable for use as the ignition source. NOTE 3: Warning--Gas pressure should not be allowed to exceed 300 mm (11.8 in.) of water pressure. 8.3 For flash points below 13C (55F) or above 60"(3 (140F), use as a bath liquid a 1+ 1 mixture of water and ethylene glycol (see Warning--Note 4). For flash points between 130C (55"F) and 600C (1400F), either water or a water-glycol mixture can be used as bath liquid. The temperature of the liquid in the bath shall be at least 10"C (18"F) below the expected flash point at the time of introduction of the sample into the test cup. Do not cool bath liquid by direct contact with dry ice (solid carbon dioxide). NOTe 4: Warning--EthyleneGlycol--Poison. Harmful or fatal if swallowed.Vapor harmful.Avoidcontactwith skin. NOTI~5--Due to possible difficultyin maintainingthe prescribed rate of temperatureriseand due to the formationof ice offthe lid, results by this methodfor sampleshavingflashpointsbelow0"C (32"F)may be unreliable. Trouble due to ice formationon the slidecan be minimized

~[~ D 56
discontinued and any result discarded. 9.3 Flash Points Below 60"C (140F)--When the flash point of the sample is known to be below 60C (140"F), apply and adjust the heat so that the temperature of the portion will rise at a rate of IC (2F)/min :1:6 s. When the temperature of the specimen in the test cup is 5C (10"F) below its expected flash point, apply the ignition source in the manner just described in 9.2 and repeat the application of the ignition source after each 0.5C (1 F) rise in temperature of the specimen. 9.4 Flash Points at 60C (140F) or Above--If the flash point of the sample is known to be 60C (140F) or higher, apply and adjust the heat so that the temperature of the specimen will rise at a rate of 3C (5F)/min + 6 s. When the temperature of the specimen in the test cup is 5C (10F) below its expected flash point, apply the ignition source in the manner just described in 9.2 and repeat the application of the ignition source each lC (2"F) rise in temperature of the specimen. 9.5 When the application of the ignition source causes a distinct flash in the interior of the cup, as defined in 3.1.1, observe and record the temperature of the specimen as the flash point. Do not confuse the true flash with the bluish halo which sometimes surrounds the ignition source during applications immediately preceding the actual flash. 9.6 Discontinue the test and remove the source of heat. the lid and wipe the thermometer bulb. Remove the test cup, empty, and wipe dry. 9.7 If, at any time between the firstintroduction of the ignition source and the observation of the flashpoint, the rise in temperature of the specimen is not within the specified rate, discontinue the test, discard the result and repeat the test,adjusting the source of heat to secure the proper rate of temperature rise,or using a modified "expected flash point," or both, as required. 9.8 Never make a repeat test on the same specimen of sample; always take fresh specimen of sample for each test.
TABLE 1
For tests

11mnnometem
At 4 to 490 (40 to 120F) 9(3 o (gF) 57C or (57F) In ~ Above 49C (120F) 9(3 or (91 =) El.

Below 4=C (40F) 570 or (571 =)

Use ASTM 11'wacme~ '~

A Gomplom ~,,;_~:~ueatiol~for these them~motem are ~

a certified reference material (CRM) such as those listed in Annex A2, which is reasonably close to the expected temperature range of the samples to be tested. The material shall be tested according to the procedure of this test method and the observed flash point obtained in 9.5 shall be corrected for barometric pressure (see Section 13). The flash point obtained shall be within the limits stated in Table A2.1 for the identified CRM or within the limits calculated for an unlisted CRM (see Annex A2.) I 1.2.4 Once the performance of the apparatus has been verified, the flash point of secondary working standards (SWSs) can be determined along with their control limits. These secondary materials can then be utilized for more frequent performance checks (see Annex A2). 11.2.5 When the flash point obtained is not within the limits stated in 11.2.3 or 11.2.4, check the condition and operation of the apparatus to ensure conformity with the details listed in Annex AI, especially with regard to tightness of the lid (Al.l.2), the action of the shutter, the position of the ignition source (Al.l.2.3), and the angle and position of the temperature measuring device (AI.I.2.4). After any adju,mnent, repeat the test in I 1.2.3 or 11.2.4 using fresh test specimen, with special attention to the procedural derails prescribed in the test method.

12. Procedure(Automated)
12.1 Adjust the external cooling system, if required, to a temperature necessary to cool the heating area 10"C below the expected flash point. 12.2 Place the test cup in position in the instrument. 12.3 When using a gas test flame, light the pilot flame and the test flame and adjust the test flame to 4 m m (5/32 in.) in diameter. If the instrument is equipped with an electrical ignition device, adjust according to the manufacturer's instructions. 12.4 Enter the Expected Flash Point; this will allow the heating area to be cooled to the required minimum starting temperature. NOTe 6---Toavoidan abnormal heating rate when the specimenis at a low temperature, it is recommendedto precoolthe test cup and cover. This may be accomplished by placing the assemblyinto position in the instrument while it is cooling to 10"C (18*F) below the programmed Expected ~ Point.
NOTe 7--Flash Point results determined in an "unknown Expected Flash Point mode" should be considered approximate. This value can be

10. Apparatus (Automated Instrument)


10.1 An automated flash point instrument is used that is capable of performing the test in accordance with Section 9, Procedure (Manual) of the test method. The apparatus can use a gas test flame or electric ignitor. The dimensions for the test cup and test cover are shown in Figs. A 1.1 and A 1.2. 10.2 Samples with low flash point may require a source of cooling for the heating area. 11. Preparation of Apparatus (Automted Instrument) 11.1 Support the tester on a level, steady table. Unless tests are made in a draR-free compartment, it is a good practice, but not required, to surround the tester with a shield to prevent draft. 11.2 The user of the automatic instrument must be sure that all of the manufacturer's instructions for calibrating, checking, and operating the equipment are followed. 11.2.1 Adjust the detection system per manufacturer's instructions. 11.2.2 Calibrate the temperature measuring device per manufacturer's instructions. 11.2.3 Verify the performance of the automated apparatus at least once per year by determining the flash point of 57

used as the ExpectedHash Point when a fresh specimen is tested in the standard mode of operation. 12.5 Using a graduated cylinder and taking care to avoid wetting the cup above the final liquid level, measure 50 + 0.5 mL of the sample into the cup, both the sample and the graduated cylinder being precooled, when necessary, so that the specimen temperature at the time of the measurement is 27 + 5"C (80 + 10"F) or at least 10"C (18"F) below the expected flash point, whichever is lower. It is essential that the sample temperature be maintained at least 10C (18F)

~
below the expected flash point during the transfers from the sample container to the cylinder and from the cylinder to the test cup. Destroy air bubbles on the surface of the specimen by use of knife point or other suitable device. Wipe the inside of the cover with a clean cloth or absorbent tissue paper; then attach the cover, with the temperature measuring device in place, to the bath collar. Connect the shutter and ignition source activator, if so equipped, into the lid housing. Readjust the size of the test flame or the setting of the electrical ignition device. Test the ignition source dipping action, if so equipped, and observe if the apparatus functions correctly. Press the start key. If a flash is observed upon initial operation, discontinue the test and discard the result. In this case a fresh specimen shall be cooled to an additional 10*C (18"17)below the original specimen installation temperature. NOTE S---Careshould be taken when cleaningand positioning the lid assembly so not to damage or dislocate the flash detection system or temperature measuring device. See manufacturer's instructions for proper care and maintenance. 12.6 The apparatus shall automatically control the test procedure as described in this test method. When the flash point is detected, the apparatus will record the temperature and automatically discontinue the test. If a flash is detected on the first application, the test should be discontinued, the result must be discarded and the test repeated with a fresh specimen. 12.7 When the apparatus has cooled down to a safe handling temperature (less than 55*(2 (130F)) remove the cover and the test cup and clean the apparatus as recommended by the manufacturer. 13. Report 13.1 Correction for barometric pressure. Observe and record the ambient barometric pressure at the time and place of the test. When the pressure differs from 101.3 kPa (760 mm Hg), correct the flash point as follows: (1) Corrected flash point ffi C + 0.25 (101.3 - p) (2) Corrected flash point = F + 0.06 (760 - P) (3) Corrected flash point ffi C + 0.033 (760 - P) where: C ffi observed flash point, *C, F ffi observed flash point, *F, p = ambient barometric pressure, kPa, and P = ambient barometric pressure, m m Hg. 13.2 The barometric pressure used in this calculation must be the ambient pressure for the laboratory at the time of test. Many aneroid barometers, such as those used at

D 56
weather stations and airports, are precorrected to give sea level readings; these must not be used. 13.3 Report the corrected flash point to the nearest 0.5C (or IF).
14. Precision and Bias 14.1 Precision--The following criteria shall be used for judging the aceeptabifity of results (95 % probability): 14.1.1 Repeatability---The difference between successive test results, obtained by the same operator with the same apparatus under constant operating conditions on identical test material, would in the long run, in the normal and correct operation of the test method, exceed the following values only in one case in twenty: Flash Point,"(2('F) Rentability, "(2('F) Below 60"C(I40"F) 1.2"(2(2.0"F) At and Above60"C(138.2"F) 1.6"(2(3.0"F)

14.1.2 Reproducibility---The difference between two single and independent results, obtained by different operators working in different laboratories on identical test material, would in the long run, in the normal and correct operation of the test method, exceed the following values only in one case in twenty: Flash Point,"(2('F) Reproducibility,"12CF) Below60"(2(140"F) 4.YC (8"F) At and Above60"C(138.2"F) 5.8"(2(10"F) 14.2 Bias--The procedure in Test Method D 56 for measuring flash point has no bias since the Tag Flash Point can be defined only in terms of this test method. The current interlaboratory tests confirm that there is no relative bias between manual and automated procedures. In any case of dispute the flash point as determined by the manual procedure shall be considered the referee test. NOTE 9--Mixtures such as, but not limited, to those that are chlorinated or include water may cause there to be significantdifferences in the results obtained by manual and automatic instruments. For these mixtures, the precision statement may not apply. NoTE 10---Theprecision data were developed in a 1991 cooperative test programII using eight (8) samples. Twelve (12) laboratoriesparticipated with the manual apparatus and seventeen (17) laboratories participated with the automatic equipment. Information on the type of samples and their averageflashpointsare in the research report available at ASTM Headquarters.
15. Keywords 15.1 combustible; fire risk; flammable; flash point; tag closed cup it Data is availablefromASTMHe~_dquarter~RequestRR:D02-1350.

58

D 56

ANNEXES (Mandatory Information) A1. APPARATUS AI.I The Tag closed tester shall consist of the test cup, lid with ignition source, and liquid bath conforming to the following requirements: A I.I.I Test Cup, of brass or other nonrusting metal of equivalent heat conductivity, conforming to dimensional requirements prescribed in Fig. AI.1. It shall weigh 68 + 1 g` AI.I.2 Lid: Al.l.2.1 The lid comprises a circle of nonmsting metal with a rim projecting downward about 15.9 mm (% in.), a slide shutter, a device which simultaneously opens the shutter and depresses the ignition source, and a slanting collar in which the cup-thermometer ferrule is inserted. Figure A 1.2 gives a diagram of the upper surface of the lid, showing dimensions and positions of the three holes opened and closed by the shutter, and the size and position of the opening for the cup thermometer. A1.1.2.2 The rim shall fit the collar of the liquid bath with a clearance not exceeding 0.4 mm (0.002 in.) and shah be slotted in such a manner as to press the lid firmly down on the top of the cup when the latter is in place in the bath. When this requirement is not met, the vertical position of the cup in the bath shall be suitably adjusted, as by placing a thin ring of metal under the flange of the cup. A1.1.2.3 The shutter shall be o~such size and shape that it covers the three openings in the lid when in the closed position and uncovers them completely when in the open position. The nozzle of the flame-exposure device, when
~: 2.0 "=~----" 6 3 . 5 - - - - - ~

used, shall conform to the dimensions given in Table A I. I. The ignition source device shall be designed and constructed so that opening the shutter depresses the tip to a point approximately 2 mm (0.08 in.) to the right of the horizontal center of the middle opening of the lid (refer to lower part of Fig. AI.3). This will bring the ignition source to the approximate center of the opening` The plane of the underside of the lid shall be between the t o p and bottom of the t i p of the ignition source when the latter is fully depressed. A 1.1.2.4 The collar for the cup-thermometer ferrule shall be set at an angle which permits placement of the thermometer with its bulb approximately in the horizontal center of the cup, at a depth prescribed in Table A 1. I. Al.l.3 Liquid Bath, conforming to the limiting or minimum dimension shown in Fig. AI.3. It shall be of brass, copper, or other noncorroding metal of substantial construction. Sheet metal of about No. 20 B&S gage (0.812 ram) is satisfactory. It may, ff desired, be lagged with heat-insulating material to facilitate control of temperature. A I.I.4 Heater, of any type (electric, gas, alcohol, etc.) capable of controlling temperature as required in Section 9. An external electric heater, controlled by a variable voltage transformer, is recommended, AI.1.5 Bath Stand--For electric heating, any type of stand may be used. For alcohol lamp or gas burner, a stand, as illustrated in Fig` 1, to protect the ignition source from air currents (unless tests can be made in a draft-free room) is required.
TABLE A1,1
Dimensional Requirements 27.8 + 0.4 mm (I .094 + 0.016 in. 29.4 + 0.8 mm (1.156 + 0.031 in. 45.0 0.8 mm (1.77 0.031 in. 54.00.1 mm (2.125 + 0.005 in. 4.0 + O.B rnm (0.156 -4- 0.031 in. 1.2 + 0.3 mm (0.049 + 0.010 in. 2.0 mm max (0.079 in. max)

+o.Ts "---54.0

Depth of I~Ul k~d surfacebelowtop of test cup


Depth of satn~e surface below top of test cup
.J

Depth of bottom of bulb of test thermometerbelow

0.5
~'0.90
~1.0

top of cup when in place


Insicle diameter of test cup Diameter ol beacl on top of cover Diameter of opermg in tip of test flame nozzle Outstcle diameter of tlp of test flame nozzle

54.5

+7,s

1
FIG. A1.1 Specimen Cup

59

D 56

+o
B -C -DE --

_ZJ
4.78 mm 15.10 mm 11.92 mm 10.32 mm ,

,iCJ
,"
I

A - - 7.15 mm

Flame Size ~ Flame Size Bead U .~djustrn~i~t Burner~ I 1 ~ Chamber

Note: All dimensions!-0.13 mm unlessotherwiseshown.


,_ 2 0 . 6

~k F - mm -'~, ,/

ID-9

84 mm

mm ,~ \~,~_

,
E E

Inch-Pound Equivalents mm 0.03 0.13 4.78 7.15 9.84 in. 0.001 0.005 0.188 0.281 0.387 mm 10.32 11.92 15.10 18.0 20.6 in. 0.406 0.469 0.594 0.71 0,81

NoTE--Dimensions relating to the size and position of the thermonteter colar are recommendedbut not mandatory. FIG. A1.2 Top of Ud Showing Position and Dimensions of Openings

95.3 mm Min. Dia.

In~-eound Squlvslem
mm 6.4 82.6 95.3 FIG. A1.3 In. 0.25 3.25 3.75

Section of Liquid Bath end Test Cup (Manual Apparatus)

60

D56

A2. VERIFICATION OF APPARATUS PERFORMANCE A2.1 Certified Reference Material (CRM)--CRM is a stable, pure (99+ mole % purity) hydrocarbon or other stable petroleum product with a method-specific flash point established by a method-specific interlabomtory study following ASTM RR:D02-1007 guidelines or ISO Guide 34 and 35. A2.1.1 Typical values of the flash point corrected for barometric pressure for some reference materials and their typical limits are given in Table A2.1 (see Note A2.3). Suppliers of CRMs will provide certificates stating the method-specific flash point for each material of the current production batch. Calculation of the limits for these other CRMs can be determined from the reproducibility value of this test method, reduced by interlaboratory effect and then multiplied by 0.7 (see Research Report RR:$15-1007). NOTE A2.1--Supporting data for the interlaboratorystudy to generate the flash point in Table A2.1 can be found in research report RR:SI5-1010.
TABLE A2.1 D 56 Typical Flash Point VMues lind Typical Limits for CRM

NOTe A2.3---Materiah, purities, flash point values and limits stated in Table A2.1 were developed in an ASTM interlaboratory program (see RR:SIS-1010) to determine $uitability of use for verification fluids in

flash point test methods. Other natedals, purities, flash point values,
and limi~l can be suitable when produced acoordin~ to the practices of

ASTM RR:D02-1007 or ISO Guides 34 and 35. Certificatesof performance of such materiah should be consultedbefore use, as the flash point value will vary dependent on the composition of each CRM batch. A2.2 Secondary Working Standard (SWS)---SWS is a stable, pure (99+ mole % purity) hydrocarbon, or other petroleum product whose composition is known to remain appreciably stable. A2.2.1 Establish the mean flash point and the statistical control limits (3#) for the SWS using standard statistical techniques. 12 NOTE A2.4---Thetypicalprocedureto arrive at the mean flashpoint is achieved by testing representative subsamples three times in an apparatus previouslyverifiedusing a CRM, statisticallyanalyzingthe results and, after outlier removal, calculatingthe arithmetical mean or by conductingan inteflaboratoryprogramwith three laboratories,each testing the representativesamplein duplicateand calculatingthe mean using standard statisticaltechniques.
IsA S T M M N L 7 Manual on the Presen~ion of Dola ControlChartAnalys~, 6th ed.,ASTM, 1990.

Hyemcmtxz
n-decane n-undecam

Pumy(moteS)
99+ 99+

Flash Po~t(C)
50.9 67.1

Um~ (f)
:1:2.3 :e2.3

A3. CHECKING CONDITION CALIIIRATION AND OPERATION OF TAG CLOSED TESTER A3.1 Material: A3.1.1 1,4 Dimethylbenzene13 (p-Xylene), conforming to the following requirements: Specific gravity (15.6/15.6"C) (60/60"F), 0.860 min~ 0.866
max.

Boiling range . . . 2"C max from start to dry point, when tested by Test Method D 850 or Test Method D 1078. The range shall include the boiling point of pure 1,4 Dimethylbenzene, which is 138.4C (281"F). Freezing p o i n t . . . 12.44C (54.4F), rain (99 % molal purity) as determined by Test Method D 1015. Contains less than 500 ppm of Ca and lighter hydrocarbons determined by gas chromatography using D 3798 (modified to allow reporting of Ce and fighter hydrocarbons) or a capillary boiling point column. n p-xylenobtainedfromany reputablechemicalsuppliermy be reed m calibratingfluidas longas theymeetthe _%~'scJ~,,mdetailedin A2.1.1.

A3.2 Procedure: A3.2.1 Determine the flash point of the 1,4 Dimethylbenzene, following the test procedures. When the tester is operating properly, a value of 27.2 :t: 0.6C (81 :t: IF) will be obtained. A3.2.2 When the flash point obtained on 1,4 Dimethylbenzene is not within the limits stated in A2.2.1, check the condition and operation of the apparatus to ensure conformity with the details listed in Annex A I, especially with regard to lightness of the lid (A1.1.2.2), the action of the shutter and the position of the ignition source (Al. 1.2.3), and the angle and position of the thermometer (Al.l.2.4). After adjustment, when necessary, repeat the test, with special attention to the procedural details prescribed in the test method. Also test a sample of Dimethylbenzene by gas chromatography to assure that it contains less than 500 ppm of Ca and hydrocarbons. Be sure to specify this level of purity.

A4. MANUFACrURING STANDARDIZATION A4.1 The cup thermometer, which conforms also to the specifications for the low-range thermometer used in the Pensky=Martens flash tester, Test Method D 93, is frequently supplied by the thermometer manufacturer with a metal or polytetrafluoroethylene ferrule intended to fit the collar on the lid of the flash tester, This ferrule is frequently supple= mented by an adapter which is used in the larger=diameter collar of the Pensky=Martens apparatus, Differences in dimensions of these collars, which are immaterial in their effect on the result of tests, are a source of considerable

61

~ ) D 56

r.i
I I I

L.,
i I i

I I

'

'I
I

I
I I
!

I
'

f 5.3 mm

8.6 mm Dia. Min.

17.3 mm

V"I
__ ! I

Packing Ring

Soft Aluminum)
8.40 mm OD 7.23 mm ID 1.5 mm Thick

]Y,;

-0.05 mm
Inch-Pound Equivalents mm 0.05 5.3 7.1 FIG. A3.1 In. 0.002 0.21 0.28 Dimensions for
Thermometer

mm 8.6 9.8 17.3

in. 0.34 0.385 0.68

Ferrule (Not Mandatory) FIG. A3.2

Inch-Pound Equlv,,lents mm in. 1.5 0.06 7.23 0.284 8.40 0.3,30 Dimensions for

Mandatory)

Thermometer

Packing Ring (Not

A4. MANUFACTURING STANDARDIZATION A4.1 The cup thermometer, which conforms also to the specifications for the low-range thermometer used in the Pensky-Martens flash tester, Test Method D 93, is frequently supplied by the thermometer manufacturer with a metal or polytetrafluoroethylene ferrule intended to fit the collar on the lid of the flash tester. This ferrule is frequently supplemerited by an adapter which is used in the larger<liameter collar of the Pensky-Martens apparatus. Differences in dimensions of these collars, which are immaterial in their effect on the result of tests, are a source of considerable unnecessary trouble to manufacturers and suppliers of instruments, as well as to users. A4.2 Subcommittee 21 on Metalware Laboratory Apparatus, of ASTM Committee E- 1 on Methods of Testing, has studied this problem and has established some dimensional requirements which are shown, suitably identified, in Figs. AI.I, A3.1, and A3.2. Conformity to these requirements is not mandatory but is desirable to users as well as suppliers of Tag closed testers.

62

~1~ D 56
The American $ooiaty for Testing and Materials takes no position respecting the validity of any patent rights asserted In connection with any item mentioned In this standard. Users of this standard are expresaly advised that determination of the validity of any such patent rights, and the risk of infringement of such rights, ere entirely their own responsibility. This standard Is subject to revision at any time by the responsible technical commlUes and must be reviewed every five years and if not ~ , alther respprovad or withdrawn. Your comments are Invited either for revision of this standard or for additional standards and should be addressed to ASTM Headquarters. Your oomments will receive careful consideration at a meeting of the responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should make your views known to the ASTM Committee on Standards, 100 Berr Harbor Drive, West Conshohockan, PA 19428.

63

(~)

Designation: D 86 - 96
Standard Test Method for Distillation of Petroleum Products 1

An American NaUonal Standard

This standard is issued under the fixed designation D 86; the number immediately following the designation indicates the year of original adoption or, in the case of revision, the year of last revision. A number in lxtrentheses indlcates the year of last reapproval. A superscript eix~lon (d indicates an editorial change since the last revision or reappmval.

This standard has been approved for use by agencies of the Department of Defense. Consult the DoD Index of Specifications and Standards for the specOtcyear of issue which has been adopted by the Department of Defense.

1. Scope 1.1 This test method covers the distillation of natural gasolines, motor gasolines, aviation gasolines, aviation turbine fuels, special boiling point spirits, naphthas, white spirit, kerosines, gas oils, distillate fuel oils, and similar petroleum products, utilizing either manual or automated equipment. 1.2 In cases of dispute, the referee test method is the manual test method prepared as directed for the indicated group. 1.3 The values stated in SI units are to be regarded as the standard. The values given in parentheses are provided for information only. 1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. 2. Referenced Documents 2.1 A S T M Standards: D323 Test Method for Vapor Pressure of Petroleum Products (Reid Method) 2 D 396 Specification for Fuel Oils2 D 850 Test Method for Distillation of Industrial Aromatic Hydrocarbons and Related Materials 3 D 975 Specification for Diesel Fuel Oils 2 D 1078 Test Method for Distillation Range of Volatile Organic Liquids 3 D 2892 Test Method for Distillation of Crude Petroleum (15-Theoretical Plate Column) 4 D4057 Practice for Manual Sampling of Petroleum and Petroleum Products 4 D 4177 Practice for Automatic Sampling of Petroleum and Petroleum Products 4 D 4953 Test Method for Vapor Pressure of Gasoline and Gasoline Oxygenate Blends (Dry Method) 5 D 5190 Test Method for Vapor Pressure of Petroleum Products (Automatic Method) 5
t This test method is under the jurisdiction of ASTM Committee D-2 on Petroleum Products and Lubricants and is the direct resl~nsibility of Subcommittee 1:}02.08 on Volatility. In the IP, this test method is under the jurisdiction of the Standardization Committee. Current edition approved Apr. 10, 1996. Published June 1996. Originally published as D 86 - 21. Last previous edition D 86 - 95. 2 Annual Book of ASTM Standards, Vol 05.0 I. 3 Annual Book of A~l'M Standards, Vol 06.04. 4 Annual Book of ASTM Standards, Vol 05.02. 5 Annual Book of ASTM Standards, Voi 05.03.

D 5191 Test Method for Vapor Pressure of Petroleum Products (Mini Method) s D 5482 Test Method for Vapor Pressure of Petroleum Products (Mini Method-Atmospheric) 5 E 1 Specification for ASTM Thermometers ~ E 77 Test Method for Inspection and Verification of Thermometers 6 E 133 Specification for Distillation Equipment 7 IP 69 Determination of Vapour Pressure-Reid Method s IP 171 Vapour Pressure Micro Method 9 3. Terminology

3.1 Definitions of Terms Specific to This Standard: 3.1.1 decomposition point--the thermometer reading that coincides with the first indications of thermal decomposition of the liquid in the flask. 3.1.1.1 Discussion--Characteristic indications of thermal decomposition are an evolution of fumes, and erratic thermometer readings that usually decrease after any attempt is made to adjust the heat. 3.1.2 drypoint--the thermometer reading that is observed at the instant the last drop of liquid evaporates from the lowest point in the flask. Any drops or film of liquid on the side of the flask or on the thermometer are disregarded. 3.1.2.1 Discussion--The end point (final boiling point), rather than the dry point, is intended for general use. The dry point can be reported in connection with special purpose naphthas, such as those used in the paint industry. Also, it is substituted for the end point (finalboiling point) whenever the sample is of such a nature that the precision of the end point (final boiling point) cannot consistently meet the requirements given in the Precision Section. 3.1.3 end point or final boiling point--the maximum thermometer reading obtained during the test. This usually occurs after the evaporation of all liquid from the bottom of the flask. The term maximum temperature is a frequently used synonym. 3.1.4 initial boiling point--the thermometer reading that is observed at the instant that the first drop of condensate falls from the lower end of the condenser tube.

6 Annual Book OfASTM Standards, Vol 14.03. 7 Annual Book OfAA'TM Standards, Vol 14.02.
t Available from The Institute of Petroleum, 61 New Cavendish St., London, WIM 8AR, England. 9 Withdrawn 1992, contact The Institute of Petroleum for availability.

64

D 86
NS 19/26

3.1.5 percent evaporated--the sum of the percent recovered and the percent loss. 3.1.6 percent loss--one hundred minus the percent total
recovery.

3.1.7 percent recovered--the volume in millilitres of condensate observed in the receiving graduate, in connection with a simultaneous thermometer reading. 3.1.8 percent recoverymthe maximum percent recovered, as observed in accordance with 9.10. 3.1.9 percent residuemthe volume of residue in millilitres measured in accordance with 9.11. 3.1.10 percent total recovery---the combined percent recovery and residue in the flask, as determined in accordance with 9.12. 3.1.11 thermometer reading--the temperature of the saturated vapor measured in the neck of the flask below the vapor tube.

line Marking

4. Summary of Test Method 4.1 A 100 mL sample is distilled under prescribed conditions that are appropriate to its nature. Systematic observations of thermometer readings and volumes of condensate are made, and from these data, the results of the test are calculated and reported. 5. Significance and Use 5.1 The distillation (volatility) characteristics of hydrocarbons often have an important effect on their safety and performance, especially in the case of fuels and solvents. Volatility is the major determinant of the tendency of a hydrocarbon to produce potentially explosive vapors. It is also critically important for both automotive and aviation gasolines, affecting starting, warmup, and tendency to vapor lock at high operating temperature or at high altitude, or both. The presence of high boiling point components in these and other fuels can significantly affect the degree of formation of solid combustion deposits. 5.2 Volatility, as it affects rate of evaporation, is also an important factor in the application of many solvents, particularly those used in paints. 5.3 Petroleum product specifications generally include distillation limits to assure products of suitable volatility performance. 6. Apparatus 6.1 Unless noted otherwise, all of the section and figure reference numbers in 6.2 through 6.8 refer to Specification E 133, the specification to which all the items listed shall conform. 6.2 Flask--Flask A (100 mL), as shown in Fig. 3 (of Specification E 133) for natural gasolines. Flask B 0 2 5 mL), as shown in Fig. 1a of this test method or as shown in Fig. 3 (of Specification E 133) for all others. 6.3 Condert~er and Cooling Bath--Section 5, and Figs. 1 and 2 of Specification E 133. 6.4 Shield--Section 6, and Figs. l and 2 of Specification E 133. 6.5 Heater--Section 7, and Figs. l and 2 of Specification E 133. 6.6 Flask Support--Table 2 (of Specification E 133),
65
Dimensions in mm
RG. l a Distillation Flask with Ground Glass Joint

GO ~' i ' ~'-"i~ t I J /

Knuded knob Cone 1:10 Male NS 19/26

if:

i i<<H
RG, l b

,.6

PTI=E Centodno Device f = ground Glass Joint

Boards A 32-ram (1.25-in.) B 38-mm (l.5-in.) or C 50-mm (2-in.) hole. 6.7 Graduated Cylinder--Section 9; Graduate B, 100 mL, as shown in Fig. 4 of Specification E 133. The cylinder must have graduations at the 5 mL level and from 90 to 100 mL in 1-mL increments. For automatic apparatus, the cylinder shall conform to the physical specifications described in this section, with the exception of the graduations. 6.7.1 For automatic apparatus, the level follower/ recording mechanism of the apparatus will have a resolution of 0.1 mL with an accuracy of:l: 1 mL. The calibration of the assembly should be confirmed according to manufacturer's instructions at regular intervals. The typical calibration procedure involves verif~ng the output with the receiver containing 5 and 100 mL of material respectively.

~) D 86
Thermometer or PT-IO0 ..~

Compression Nut

1 =i

6.8.2 The temperature sensor shall be mounted through a snug-fitting device designed to mechanically center the sensor in the neck of the flask. The use of a cork or silicone stopper with a hole drilled through the center is not acceptable for this purpose. Examples of acceptable centering devices are shown in Figs. l and 2. 7. Sampling 7.1 Determine the GROUP characteristics that correspond to the sample to be tested (see Table l). Where the procedure is dependent upon the group the section headings will be so marked. 7.2 Sampling shall be done in accordance with Practice D 4057 or Test Method D 4177 and as described in Table 2. 7.2.1 GROUP 0--Collect the sample in a bottle previously cooled to 0 to 4.5C (32 to 40F) preferably by immersing the bottle in the liquid, where possible, and discarding the first sample. Where immersion is not possible, the sample shall be drawn off into the previously cooled bottle in such a manner that agitation is kept at a minimum. Close the bottle immediately with a tight-fitting stopper and place the sample in an ice bath or refrigerator to maintain the sample at that temperature. 7.2.2 GROUPS 1 and 2--Collect and maintain the sample as described in 7.2.1 at a temperature of 0 to 10C (32 to 50"F). 7.2.3 GROUPS 3 and 4--Maintain the sample at ambient temperature. I f sample is not fluid at ambient temperature, it is to be maintained at a temperature of 11C (20F) above its pour point. 7.3 Samples of materials that visibly contain water are not suitable for testing. 7.3.1 GROUPS 0, 1, and 2--If the sample is not dry, obtain another sample that is free from suspended water for the test. 7.3.2 GROUPS 3 and 4--In cases where a water free sample is not practical, the suspended water can be removed by shaking the sample with anhydrous sodium sulfate or other suitable drying agent and separating it from the drying agent by decanting. 8. Preparation of Apparatus 8.1 Refer to Table 3 and prepare the apparatus as directed for the indicated group. Bring the temperature of the graduate, the flask, the temperature sensor, and the cooling bath to the indicated temperature. 8.2 Make any necessary provisions so that the temperature of the cooling bath and the graduate will be maintained at their respective temperatures. The cooling bath must have a liquid level above the highest point of the condenser. If necessary, make suitable provision for circulation, stirring, or air blowing to provide a uniform temperature throughout the bath. The graduate must be in a bath such that either the liquid level is at least as high as the 100 mL mark, or the entire graduate is surrounded by an air circulation chamber. 8.2. I GROUPS 0, 1, 2, and 3--Snitable media for low temperature baths include chopped ice and water, refrigerated brine, and refrigerated ethylene glycol. 8.2.2 GROUP 4--Suitable media for ambient and higher bath temperatures can include cold water, hot water, or heated ethylene glycol. 8.3 Remove any residual liquid in condenser tube by 66

Threads

Compression O-Ring j~. e PTFE Body I

"

./

I
Neck of Distilling Flask

m m m

Double O-Rings 41 Viton or Perfluorof L, Elastomer.

Flask ID to be Precision Bore

FIG. 2 Centering Device for Straight-Bore Neck

6.8 Temperature Sensor--Section 10 of Specification E 133, ASTM Thermometers 7C (71=) and 8C (8F) or IP Thermometers 5C (low distillation) and 6C (high distillation) conforming to the IP Specifications for Standard Thermometers. Under certain test conditions the bulb of the thermometer can be 28"(3 (501=) above the temperature indicated, and at an indicated temperature of 371C (700"1 the tempera=) ture of the bulb is approaching a critical range in the glass. Thermometers that have been exposed to such conditions are not to be reused without checking their ice point to verify calibration as prescribed in Specification E 1 and Test Method E 77. 6.8.1 Temperature measurement systems using thermocouples or resistance thermometers must exhibit the same temperature lag and accuracy as the equivalent mercury in glass thermometer. Confirmation of the calibration of these temperature sensors is to be made on a regular basis. This can be accomplished potentiometricagy by the use of standard precision resistance, depending on the type of probe. Another technique is to distill pure toluene in accordance with Test Method D 850 and compare the temperature indicated with that shown by the above mentioned mercury in glass thermometers when carrying out a manual test under the same conditions. NOTE l--When running the test by the manual method, products with a low initialboilingpoint may have one or more readingsobscured by the centeringdevice. NOTe 2--Toluene is shown in reference manuals as boiling at 110.6"Cunder the conditionsof Test MethodD 1078 that uses a partial immersionthermometer.Becausethis test methodusestotal immersion thermometers the results will be lower and different with each. The approximate figures are Thermometer 7C (TF) or IP 5C at 109"C (228"F), and Thermometer8C (8F) or IP 6C at 110"C(230"F).

~1~ D 8 6
TABLE 1 Group 0 Sample Characteristics: Distillate Type: Vapor pressure at 37.8C, kPa 100F, psi (Test Methods D 323, O 4953, D 5190, D 5191, D 5482, IP 69 or IP 171) Dlst~latlon, IPB C F EP C F Natural Gasoine > 65.5 > 9.5 < 65.5 < 9.5 < 65.5 < 9.5 ~1~ s212 >250 > ~2 < 65.5 < 9.5 >1~ >212 >2~ >482 Group Characteristics Group 1 Group 2 Group 3 Group 4

s250 s482 TABLE 2 Sampling

s250 s482

Temperature of Sample Bottle: oC F Tempembxe of Stored Sarape: oC F If esmple Is wet:

Group 0 0 to 4.5 32 to 40 0 to 4.5 32 to 40 Resample

Group I 0to10 32 to 50 0to10 32 to 50 Resample

Group 2

Group 3

Group 4

0to10 32 to 50
Res~p~

Ambient Ambient 11C alx~vepour point ~ Ambient 20eF above pour point Dry in _-l:~--~moe Dry in with 7.3.2 with 7.3.2

~0
Flesk, ml. ASTM Dbthtion IP DisSlatkxl ~ 100

T~31W~l~ratlon~~s ~1
125

~2
125

~3
125

~4
125

7c FF)
5C A 32 (1.25)

7C p'F)
5C B 38 (1.5)

7C FF)
5C B 38 (1.S)

7C (7F)
5C C 50 (2.0)

eC (eF)
6C C 50 (2.0)

Sup~xt Dt.mter of ho~, mm ~n.)

Temperature at start of Test: FIMk and thermometer, C =F

o to4.5
32 to40 Not W~'

13to is
53 to 65 Not~

13to 18
s6 to65 Not ~ o v e

Fmk ~ a o r t and ~e~


GrlKluate and 100 mL charge, oC F

13to is ss to65
Not ~ v e

Not'hOve amUent
...

0 tO 4.5 32 tO 40

~ 13 tO 18 55 tO 65

xm~nt 13 tO 18 55 tO 65

13 tO 18 55 tO 65

13 tO llmblent 55 tO Ilnlblent

swabbing with a piece of soft, tint-free cloth attached to a cord or copper wire. 8.4 GROUPS 0, 1, 2, and 3--Fit a thermometer 7C (7F), prodded with a snug-fitting, well-rolled cork or siliconerubber stopper, tightly into the neck of the sample container and bring the temperature of the sample to the temperature indicated in Table 3. 8.5 Measure 100 mL of sample in the graduate and transfer as completely as practical the contents of the graduate to the distillation flask, taking care that none of the liquid flows into the vapor tube. 8.6 Fit the temperature sensor through a snug.fitting device designed to mechanically center the sensor in the neck of the flask. In the case of a thermometer, the bulb is centered in the neck and the lower end of the capillary is level with the highest point on the bottom of the inner wall of the vapor tube (see Fig. 3). In the case of thermocouple/ resistance thermometer, follow the manufacturer's instructions as to placement. 8.7 Fit the flask vapor tube, provided with a snug-fitting, well-rolled cork or silicone rubber stopper, tightly into the condenser tube. Adjust the flask in a vertical position and so that the vapor tube extends into the condenser tube for a distance of 25 to 50 mm (1 to 2 in). Raise and adjust the flask support board to fit snugly against the bottom of the flask. 8.8 Place the graduate that was used to measure the 67

charge, without drying, into its bath under the lower end of the condenser tube so that the end of the condenser tube is centered in the graduate and extends therein for a distance of at least 25 m m (1 in), but not below the 100-mL mark. Cover the graduate closely with a piece of blotting paper, or similar material, that has been cut to fit the condenser tube snugly. 8.9 Record the room temperature and prevailing barometric pressure. Proceed at once with the distillation, as given in the Procedure Section.

RG. 3

Position of Thermometer in Distillation Flask

D 86
9. Procedure 9. I Apply heat to the distillationflask and contents. The heating at this stage must be so regulated that the time interval between the firstapplication of heat and the initial boiling point is as indicated in Table 4. 9.2 Observe and record the initial boring point. If a receiver deflector is not being used, immediately move the graduate so that the tip of the condenser touches its inner wall. 9.3 Regulate the heating so that the time from initial boiling point to 5 or I0 % recovered is as indicated in Table 4. 9.4 Continue to regulate the heating so that the uniform average rate of condensation from 5 or I0 % recovered to 5 m L residue in the flask is 4 to 5 m L per rain. 9.5 Repeat any distillationthat did not meet the foregoing conditions. 9.6 If a decomposition point is observed, discontinue the heating and proceed as directed in 9. I0. 9.7 In the interval between the initial boiling point and the end of the distillation,observe and record data necessary for the calculation and reporting of the results of the test as required by the specification involved, or as previously established for the sample under test. These observed data can include thermometer readings at prescribed percentages recovered, or percentages recovered at prescribed thermometer readings, or both. Record all volumes in the graduate to the nearest 0.5 or 0. I mL, and all thermometer readings to the nearest 0.5"C (l.0F) or 0.1"C (0.1F) as appropriate to the apparatus being used. 9.7.1 G R O U P 0--1n cases in which no specific data requirements have been indicated, record the initialboiling point, the end point (final boring point) and thermometer readings at each I0 % multiple of volume recovered from I0 to 90, inclusive. 9.7.2 G R O U P I, 2, 3, and 4--1n cases in which no specific data requirements have been indicated, record the initial boring point, the end point (final boring point) or dry point, or both, and thermometer readings at 5, 15, 85 and 95 % recovered, and at each 10 % multiple of volume recovered from 10 to 90, inclusive.
TABLE 4 Group 0 Temperature of cooling bathA, =C F Temperature of bath around graduate, C F Tlrne from first appfcatlon of heat to Initial boiling point, minutes Time from initial boiling point to 5 '~ recovered, seconds to 10 ~ moovemd, minutes Unlfotm everage rate of condensation from 5 'J; reoovemd to 5 mL residue In flask, mL/rnln Time reoorded from 5 mL resldua to end point, min 0 to 1 32 to 34 0 to 4 32 to 40 2 to 5 ... 3to4 4to5 3to5

9.7.3 If it is required to report the thermometer reading at a prescribed percent evaporated or recovered for a sample which has a rapidly changing slope of the distillation curve in the region of the prescribed percent evaporated or recovered reading, record temperature readings at more frequent intervals. Intervals as small as every 1% recovered may be required depending on the magnitude of the change of slope. The slope is considered rapidly changing if the Change in Slope (C) is greater than 0.6 [Change of Slope (F) is greater than l.O] as calculated by Eqs (1) and (2)]. Change of Slope (C)
I [(C= -- C|)/(V 2 -V|)] -- [(C3 - -C,m]I)/(V~

-- V = ) ]

([)

Change of Slope (F) - [(F, - F,)I(V z - V,)] - [(F, - F=)I(V, - V2)] (2) where: C! = Temperature at the volume % recorded one reading prior to the volume % in question, "(3, Temperature at the volume % recorded in question, "C, c 3 = Temperature at the volume % recorded following the volume % in question, C, Temperature at the volume % recorded one reading F1 prior to the volume % in question, F, F2 Temperature at the volume % recorded in question, "F, Temperature at the volume % recorded following the volume % in question, "F, v , = Volume % recorded one reading prior to the volume % in question, V2 = Volume % recorded at the volume % in question, and V3 ffi Volume % recorded following the volume % in question. 9.8 When the residual I/quid in the flask is approximately 5 mL, make a final adjustment of the heat so that the time from the 5 mL of liquid residue in the flask to the end point (final boiling point) shall be within the limits prescribed in Table 4. If this condition is not satisfied, repeat the test, with appropriate modification of the final heat adjustment. 9.9 Observe and record the end point (final boiling point) or dry point, or both, as required, and discontinue the heating.
=

Conditions During Test Procedure Group I 0to1 32 to 34 13 to 18 55 tO 65 5to10 60 to 75 4to5 3~5 Group 2 0to4 32 to 40 13 to 18 55 to 65 5tO10 60 to 75 4to5 3~5 Group 3 0to4 32 to 40 13 to 18 5 to 65 5to10 Group 4 0to60 32 to 140 :t 3 :1:5 of charge 5to15

ta~0a~um

o.

4to5 5max

4to5 5max

'~The ixoper condenser bath temperature wa depend upon the wax content of the sample and of Its distillation fractions. The minimum temperature that permlts satlsfacto~/opwstlon shall be used. In general, a bath tomperature In the 0 ~ 4C (32 ~ 40~ ~ ~~ ~ k ~ ~ ~ ~ ~ ~ ~ Grade No. I fuel olI as pmscrlbed in Sl)ecif~a~on D 396, and those meeting the speclflcatk:ns ~ ~ ~. I~ ~ ~ ~ ~ ~ ~~ D 975. ~ ~ cases involvlng Grade No.2 fu~ oi (see Speciflcatlon D 396), Grade No. 2.D dlesel fual oU (see S ~ t J o n D 975), gas oils and slmllar d l s ~ , ~ ~y ~ ~ to hold the condenser bath temperature at some point in the 38 to 60C (100 to 140F) range, in order to avoid the o'lensatlon of solid waxy matodals in the condenm" tube.

68

~
9.10 While the condenser tube continues to drain into the graduate, observe the volume of condensate at 2 min intervals until two successive observations agree. Measure this volume accurately, and record it, to the nearest 0.5 or 0. l mL as appropriate to the apparatus being used, as percent recovery. If the distillation was previously discontinued under the conditions of a decomposition point, deduct the percent recovery from 100, report this difference as percent residue and loss, and omit the procedure given in 9.11. 9.11 After the flask has cooled, pour its contents into a 5 mL graduated cylinder, and with the flask suspended over the 5 mL graduate, allow the flask to drain until no appreciable increase in the volume of liquid in the 5 mL graduate is observed. 9.11. l GROUP 0--Cool the graduate to 0 to 4.5"C (32 to 40"F). Record the volume in the graduate, to the nearest 0.1 mL, as percent residue. 9.11.2 GROUPS 1, 2, 3, and 4---Record the volume in the graduate, to the nearest 0.1 mL, as percent residue. 9.12 The sum of the percent recovery (see 9.10) and the percent residue (see 9.11) is the percent total recovery. Deduct the percent total recovery from 100 to obtain the percent loss.
10. Calculations and Report

D86
IP Thermometer 5C can be reported in place of the obscured ASTM Thermometer 8C (8F) or IP Thermometer 6C readings, and the test report shall so indicate. If, by agreement, the obscured readings are waived, the test report shall so indicate. 10.3 Thermometer readings shall be corrected to 101.3 kPa (760 mm HI;) pressure except when product definitions, specifications, or agreements between the purchaser and the seller indicate, specifically, that such correction is not required or that correction shall be made to some other base pressure. This report shall include the observed pressure and shall state whether corrections have or have not been applied. When the report is based on thermometer readings corrected to 101.3 kPa (760 mm Hg), obtain the correction to be appfied to each thermometer reading by means of the Sydney Young equation as given in Eqs. 3, 4, or 5, or by the use of Table 5. For Celsius temperatures:
C c - 0.0009 (I01.3 - Pk)(273 + tc) Cc = 0.00012 (760 - PX273 + tc) For Fahrenheit temperatures: (3) (4)
(5)

c:where: C# and

0.00012 (760 - PX4~o +

t:)

10.1 For each test, calculate and report whatever data are required by the specification involved, or as previously established for the sample under test (see 9.7). Report all percentages to the nearest 0.5 or 0.1, and all thermometer readings to the nearest 0.5"C (I.0"F) or 0.1"C (0.1"F) as appropriate to the apparatus being used. Report the barometric pressure to the nearest 0.1 kPa (l mm Hg). 10.2 GROUP 4--When ASTM Thermometer 8C (SF) or IP Thermometer 6C is used in testing aviation turbine fuels and similar products, pertinent thermometer readings can be obscured by the cork. To provide the desired data, a second distillation according to Group 3 may have to be performed. In such cases, reading from ASTM thermometer 7C (7F) or
TABLE 5 Approximate Thermometer Reading Corrections ~ A per 1.3 kPa (10 mm) Dlfbmnce fn _Pr,~,_,re _ "C "F 0.35 0.38 0.40 0.42 0.46 0.47 0.50 0.52 0.54 0.57 0.59 0.62 0.64 0.66 0.69 0.71 0.74 0.78 0.78 0.81 0.63 0.98 0.72 0.76 0.81 0.85 0.90 0.94 0.98 1.03 1.06 1.12 1.15 1.19 1.24 1.28 1.33 1.37 1.40 1.46

corrections tO be added algebraically to the observed thermometer readings t# or th respectively, Pk = barometric pressure, kPa, prevailing at the time and location of the test, and P : barometric pressure, mm H~, prevailing at the time and location of the test. After applying the corrections and rounding each result to the nearest 0.5"C (1.0"F) or 0.1"C (0.1"F) as appropriate to the apparatus being used, use the corrected thermometer readings in all further calculations and reporting. 10.4 After barometric corrections of the thermometer readings have been made, if required (see 10.3), the following data require no further calculation prior to reporting: initial boiling point, dry point, end point (final boiling point), decomposition point, and all pairs of corresponding values
TABLE 6

C/:

Values of Constants A and B Used in Obtaining


Corrected DlsUllation Le_-_-

Temperature Range "C 10 tO 30 30 to 50 50 to 70 70 to 90 90to 110 1I0 to 130 130 to 150 150 tO 170 170 to 190 190 tO 210 210 to 230 230 to 250 250 to 270 270 tO 290 290 to 310 310 tO 330 330 to 380 350 tO 370 370 tO 390 390 to 410 "F 50to 86 86to 122 122 to 158 158 to 194 134to 230 230 tO 266 266 to 302 302 to 338 338 to 374 374 to 410 410 to 446 446to 462 482to 518 518to 554 554 to 590 590to 626 638tO 982 662 tO 698 698to 734 734to 770

Otwn~d EWm~etflc P r m g n kPa mm Hg 74.6 76.0 77.3 78.6 50.0 81.3 82.6 84.0 e5.3 86.6 88.0 89.3 90.6 92.0 93.3 94.6 96.0 07.3 98.0 100.0 101.3 560 57O 580 580 500 610 620 630 640 650 660 670 680 690 700 710 720 730 740 750 760

A 0.231 0240 0~58 0.261 0.273 0.286 0.300 0.316 0.333 0.353 0.375 0.400 0.428 0.461 0.500 0.545 0.50O 0.687 0.750 0.857 1.000

B 0.384 0.38O 0.375 0.369 0.363 0.357 0.350 0.342 0.333 0.323 0.312 0.300 0.286 0.269 0,250 0.227 O2OO 0.166 0.125 0.071 0.000

A TO be added when Imromelrlc pmuure Is below I01.3 kPa (750 mm l-lg); to be subtrm:~Kl when ~ pmuure Is AbOVeI01.3 IdNi (750 mm Hg).

69

D 86
involving percentages recovered and thermometer readings. 10.5 When thermometer readings are corrected to 101.3 kPa (760 mm Hg) pressure, the actual loss shall be corrected to 101.3 kPa (760 mm Hg) pressure, according to the following equation: L c ffi A L + B (6) ffi percent loss as calculated from test data, Lc = corrected loss, and A and B = numerical constants. 10.5.1 The values of A and B that depend upon the prevailing barometric pressure are listed in Table 6. The following equation can be substituted: Lc ffi {(L - 0.499287)/(13.65651 - 0.12492914 Pk)} (7) + 0.4997299 Lc ffi ((L - 0.499287)/(13.65651 - 0.01665174 P)} (8) + 0.4997299 where: L = percent loss as calculated from test data, Lc ffi corrected loss, Pk ffi pressure, kPa, and P = pressure, mm Hg. 10.5.2 The corresponding corrected percent recovery is calculated according to the following equation: R c ffi R + ( L - L) (9) where: L = observed loss, Lc ffi corrected loss, R -- observed recovery, and Rc ffi corrected recovery. 10.5.3 When the thermometer readings have not been corrected to 101.3 kPa (760 mm Hg) pressure, the percent residue and percent loss are to be reported as observed in accordance with 9.11 and 9.12 respectively. 10.5.4 When reporting data, state whether the corrections have or have not been applied. 10.5.5 The corrected loss shall not be used in the calculation of percentages evaporated. 10.6 It is advisable to base the report on relationships between thermometer readings and percentages evaporated in any case in which the sample is a gasoline, or any other product classed under GROUP 1, or in which the percent loss is greater than 2.0. Otherwise, the report can be based on relationships between thermometer readings and percentages evaporated or recovered. Every report must indicate dearly which basis has been used. 10.7 To report percentages evaporated at prescribed thermometer readings, add the percent observed loss to each of the observed percentages recovered at the prescribed thermometer readings, and report these results as the respective percentages evaporated, that is: P, = P, + L (10) where: L -- observed loss, Pe ffi percentage evaporated, and P, = percentage recovered. 10.8 To report thermometer readings at prescribed percentages evaporated, use either of the two following proce70 where: L
TABLE 7 Evaporated Point IBP 5',r, Repeatability and Reproducibility for Group 1 (Manual) Repeatab~llty A *C F 3.3 ro + 0.66
ro ro ro

ReWoduclbMtyA C F 5.6 Ro + 1.11


Ro Ro - 1.22 Ro - 0.94

6 re + 1.2
ro ro ro

10 Ro + 2.0
Ro Ro - 2.2 Ro - 1.7

10 to80% 90 ~; 95
FBP

3.9

7.2

13

Read ro and Ro from the graph ln either Ftg. 4 ('C) or Ftg. 5 ('F).

dures, and indicate on the report whether the graphical procedure or the arithmetical procedure has been used. 10.8.1 A r i t h m e t i c a l P r o c e d u r e . - - D e d u c t the observed distillation loss from each prescribed percentage evaporated in order to obtain the corresponding percentage recovered. Calculate each required thermometer reading as follows: T= Tt.+
(T+l - T L X R - RL)

RH - Rl,

(11)

where: R ffi percent recovered corresponding to the prescribed percent evaporated, R H = percent recovered adjacent to, and higher than R, RL - percent recovered adjacent to, and lower than R, T ffi thermometer reading at the prescribed percent evaporated. TH ffi thermometer reading recorded at RH and T L = thermometer reading recorded at R L. Values obtained by the arithmetical procedure are affected by the extent to which the distillation graphs are nonlinear. Intervals between successive data points can, at any stage of the test, be no wider than the intervals indicated in 9.7. In no case shall a calculation be made that involves extrapolation. 10.8.2 Graphical P r o c e d u r e - - U s i n g graph paper with uniform subdivisions, plot each thermometer reading corrected for barometric pressure, if required (see 10.3), against its corresponding percent recovered. Plot the initial boiling point at 0 % recovered. Draw a smooth curve connecting the points. For each prescribed percent evaporated, deduct the distillation loss, in order to obtain the corresponding percent recovered, and take from the graph the thermometer reading which this percent recovered indicates. Values obtained by graphical interpolation procedures are affected by the care with which the plot is made.
NOTE 3--See AppendixX ! for numericalexamplesillustratingthese arithmeticalprocedures. I I. Precision and Bias

II. I The precision of this test method as determined by the statistical examination of interlaboratory test results is described below. Table A I. I lists which tables and figures are to be used for the different fuel groups, distillation methods, and temperature scales. 11.2 Repeatability: I 1.2. I GROUP 0--With proper care and strict attention to details, duplicate results obtained for endpoint should not differ from each other by more than 3.5"C (6"F). Differences in duplicate temperature readings for each prescribed percentage point should not exceed the amounts equivalent to 2 mL of distillate at each point in question.

41~ D 86
1011

J
..
I/" j~
J
4
3 2

J J
f

11 10 II. IlL 7 ~

/,//~ ,/
f

J J
f j l
6~ 4 ~ 3 :t I

J J
f

f
j

J
~ J

0
0.5 I.O 1.5 2.0 2.5 3.0 3.S 4.0

0 O.S 1~ 1A 3.~ 4i 3.0 3JI 4JI 4,8

"CIV%
NOTE-FIG. 4

"C/V~
NOTE-r o - 0.873 (C/V %) + 1.131 (18) Ro - 1.998 {C/V %) + 2.617 (19) GROUP 1--Repeatability, ro l i n d Reproducibility, Ross

ro - 0.864 (C/V %) + 1.214 (14) ,, 1.736 (C/V %) + 1.994 (15) GROUP lmRepeatability, r o and Reproducibility, Res
Ro

FIG. 6
:'Z Z0 15

Z2, 20. 18.

J
o

t4, 12

f
O

16 -14 O 12

Ro

/
_ I

Ro /

.J
l

O t.

10 8 $ 4 Z 0 0
NOTE m

O z..

8 S 4
va

.J
f
j
f

J
ro

2 6 Y 0 I 0 0 NOTE.~
FIG. 7

ro 1 2 3 4 5 G ? 8 9

F/V%

F/V%
%) + 2.036 (20) %) + 4.711 (21) GROUP 1--Repeatability, re and Reproducibility, Rols TABLE 9 Repeatability and Reproducibility for Groups 2, 3, and 4 ( A u t o m a t )
ro - 0.673 ('F/V Ro - 1.998 (*F/V

FIG. S

%) + 2.186 (18) %) + 3.589 (17) GROUP l mRepeatabiUty, r o and Reproducibility, Rs Repeatability and Reproducibility for Group 1

r o - 0.864 (F/V Ro - 1.736 (F/V

TABLE 8 Evaporated Point IBP


5 %

(A.tom~)
Repeatab~ A C F 3.9
r o + 1.0 r o + 0.56

ReproducibilityA C F 7.2
Ro + Ro +

S
Colected IBP 2% 5% 10% 20 to 70 % 80% 90 to 95 % FBP C

R(meatab~A
F 8.3 6.3 2.0 + 1.08 S 2.2+1.425 2.2 + 1.42 S 2.2+1.425 2.0 + 1.08 S 6.3 3.5 3.5 1.1 + 1.08 S 1.2 + 1.42S 1.2 + 1.42 S 1.2+1.425 1.1 + 1.08 S 3.5

ReWodudb~A
C 8.5 2.6 + 1.92 S 2.0 + 2.53 S 3.0+2.645 2.9 + 3.97 S 3.0+2.645 2.0 + 2.53 S 10.5 F 15.3 4.7 + 1.92 $ 3.8 + 2.53 S 5.4+2.645 5.2 + 3.97 S 5.4 + 2.94 S 3.6 + 2.53 $ 18.9

7
r o + 1.8 ro + 1.0

13
Ro +

10 % 20 % 30 to70%
80 % 90%

ro
ro ro ro r o + 1.4

ro
ro ro ro ro +

1.78 0.72 Ro + 0.72

3.2 Ro + 1.3 Ro + 1.3

95 % FBP

2.5 F~.

Ro R o - 0.94 Ro-1.9 Ro

Ro Ro - 1.7 Ro-3.5 Ro

4.4

8.9

16

"ReadroandRofrOmU~egraphIn ~th~

5 (o)or Rg. 7 ('F).

A S IS the ilverage idope calculated In _.wx~darce wflh 11.4. ___ twenty.

11.2.2 GROUP 1--The difference between successive results obtained by the same operator with the same apparatus under constant operating conditions on identical test material would, in the long run, in the normal and correct operation of this test method, exceed the values indicated in Table 7 (Manual) or Table 8 (Automatic) in one case in
91

11.2.3 GROUPS 2, 3, and 4--The difference between successive results obtained by the same operator with the same apparatus under constant operating conditions on identical test materials would in the normal and correct operation of this test method, exceed the values indicated in

~
R(P(ATAIllLITY RLrpRoDucIBILITY

D 86
R(P(ATABILIT Y REPRODUCIBILITY -8

'7

'[ 'I

'-.0
s-

"1

o "J
1 E T P I

I~ E T

( NOTE~ I .= ~

P
boiling point, F,

NOTE---I " Initial boiling point, C, E .. end poklt (final boiling point) or dry point, oC, T = thermometer reading at Wescdbed percent evaporated or recovered0 "C, and P -- pe,-~nt evaporated or recovered at prescribed thermometer reading, C. FIG. 8 Groups 2, 3, 4 - - M a n u a l Method-Celsius Preclslon of Distillation Test Method O 86 - IP 123

E = end Point(f~J ~

p~nt) or dry p~nt, F,

T = thermometer reading at prescribed percent evaporated or recovered, F, and P - percent evaporated or recovered at prescribed thermometer reading, F. FIG. 9 Groups 2, 3, 4 ~ M a n u a l Method-Fahrenheit Precision of Distillation Test Method D 86 - IP 123

Fig. 8 (Manual, C) or Fig. 9 (Manual, "F) or Table 9 (Automatic) in one case in twenty. 1'1s

11.3 Reproducibility:
11.3.1 GROUP l m T h e difference between two single and independent results obtained by different operators working in different laboratories on identical test material would in the normal and correct operation of this test method, exceed the values indicated in Table 7 (Manual) or Table 8 (Automatic) in one case in twenty. 11.3.2 GROUPS 2, 3, and 4--The difference between two single and independent results obtained by different operators working in different laboratories on identical test material would in the normal and correct operation of this test method, exceed the values indicated in Fig. 6 (Manual, "C) or Fig. 8 (Manual, "F) or Table 9 (Automatic) in only one case in twenty, t.st 11.4 To facilitate the use of the tables and figures, the rate
~oTest Method D 86 Manual Method North American and IP Lat~ '~ Test Method D 86 Automatic Method North American and IP L a ~

of change in thermometer readings in degrees Celsius (Fahrenheit) per the percentage recovered, at any point between the 10 and 90 % point, is assumed to be the same as the average rate between two data points that are equidistant above and below the point in question. The span from the point in question to either of the other data points does not represent more than 10 % recovered in any case, nor more than 5 % if the point in question is the 5 % point. Precision values for typical values of slope for GROUPS 2, 3, and 4 (Automatic) are given in Table 10. 11.4.1 The equations that follow are used as guidelines in calculating C/V % (F/V %). In the event the distillation end point occurs prior to the 95 % point, then appropriate modifications to the use of these equations must be made. 11.4.2 For Group 1 in the manual method and for all groups in the automatic method, the initial boiling point and end point do not require C/V % (F/V %). 11.4.3 For Groups 2, 3, and ~; in the manual method, the rate of change in thermometer readings in degrees Celsius per percentage recovered should be calculated from the nearest reading (5 % in the case of the IBP, and either 90 or 72

@
95 % in the case of FBP) and the corresponding IBP or FBP. 11.4.4 5 % recovered is calculated as follows:

D 86
TABLE 10
Collect~ 20 to 70

Observed Precision Values for Typical Values of Slope Groups 2, 3, and 4 (AutomaUc)
Slope *C/XV *F/XV 0,5 1,0 1.5 2.0 2.5 0.5 1.0 1.5 2.0 2~ 1.0 2.0 3.0 4.0 2.0 3.0 4.0 5.0 ...... ...... 0,9 1.8 2.7 3.6 4.5 0.9 1.8 2.7 3.6 4.5 1.8 3.6 5.4 7.2 3.6 5.4 7.2 9.0 Repeatabll~ *C *F 1.5 2.5 3,0 4,0 4.5 1.5 2.5 3.0 4.0 4.5 2.0 3.0 4.0 5.0 3.5 3.5 3.5 3.5 3.5 3,5 2.7 4,5 5,4 7.2 8.1 2.7 4.5 5.4 7.2 8.1 3.6 5,4 7.2 9.0 6,3 6.3 8.3 6.3 6.3 6.3 Re~ucl~l~ *C *F 4.5 6.5 8.5 10.5 12.5 4.0 5.5 7.0 8.0 9.5 4.5 7.0 9.5 12,0 6.0 8.0 10.0 12.0 8.5 10.5 8.1 11.7 15.3 18.9 22.5 7.2 9,9 12.6 14.4 17.1 8.1 12.6 17.1 21.6 10.8 14.4 16.0 21.6 15,3 18.9

C/V%, F/V% 0.1(Tm - TIBP) (12) 11.4.5 10 tO 80 % recovered is calculated as follows: C/V%, FlY% -- 0.05(T(v+lo) - T(v_lo)) (13) 11.4.6 90 % recovered is calculated as follows: C/V%, FlY% 0.1(Tgo ?'so ) (14) 11.4.7 95 % recovered is calculated as follows: (15) C[V%, F/V% = 0.2(7"95 - T9o) where: C/V% = rate of change in temperature at the volume percent in question, *C, F/V% = rate of change in temperature at the volume percent in question, *F, and T = temperature at the percent volume recovered indicated by the subscript, *C or *F, subscripts: V = volume percent recovered in question, V - I0 = 10 % less than volume percent in question, V + I0 = I0 % more than volume percent in question, and IBP, 5, I0, 80, 90, 95 = appropriate volume percent indicated. 11.5 Bias: I 1.5. l Absolute Bias--Due to the use of total immersion thermometers or temperature sensing systems designed to emulate them, the distillation temperatures in this test method are somewhat lower than the true temperature. The amount of absolute bias has not been determined.
: =
- -

10 and 80 Y.

5, 90, and 95 ~.

2~

IBP FBP

11.5.2 Relative Bias--There exists a bias between the empirical results of distillation properties obtained by this test method and the true boiling point distillation curve obtained by Test Method D 2892. The amount of relative bias between the two test methods has not been determined. 11.5.2.1 Groups 1, 2, 3, and 4mRefer to Tables AI.2 A I.3, and A 1.4 for the statement of bias between automatic and manual apparatus. 12. Keywords 12.1 distillates; distillation; petroleum products

ANNEX

(Mandatory Information)
TABLE A1.1
Group
0 1 1 2,3,4 2,3,4

Summary of Aids for Definition of Repeatability and Reproducibility


Distillation Method Manual or Automatic Manual Automatic Manual Automatic Temperature Scale *C or=F =C OF C F C OF C F Table, Section, and Figureto Use 11.2.1 Table 7 and Fig. 4 Table 7 and Fig. 5 Table 8 and Fig. 6 Table 8 and Fig. 7 Fig. 8 Fig. 9 Tables 9 or 10 Tables 9 or 10

73

(~) D 86
TABLE A1.2 Condensed Summary of C o m p a r a t i v e Manual and Automatic Distillation Results NOTE---All thermometer readings were oerrected to 101.3 kPa (760 mm Hg) pressure. The left-hand figures were manually obtained, and the right-hand figures represent commpond~g resu~ from the automatic apparatus. Celsius Gaso/ine.--Twenty six laboratories and fourteen samples (see Table A1.3) Kerosine--Eight tests in four laboratories for manual, and six tests in three laboratodes for automatic 176.5, 174.5 193.5, 193 215.5, 215.5 248, 248.5 171.5, 172 191, 193.5 213.5, 214 245.5, 248.5 174.5, 173.5 191.5, 191.5 214.5, 214.5 245, 247 Diesel Fuel--Ten tests in five laboratorkls for manual and for autornat~ 190.5, 189 215, 218 268.5, 269 322, 323 179.5, 179.5 208.5, 208.5 264, 264 318, 316 185.5, 134.4 213, 214 266, 266 319.5, 318.5 Fahrenheit
Gasoline---Twenty six laboratories and fourteen samples (See Table A1.4) Initial Boiling 10 50 ~ 90 Point Evaporated Evlq~xlltsd Evaporated Keros/ne---EIght tests In four labomtodw for manual, and six tests In three laboraterles for automatlo 350, 346 380, 379 420, 420 478, 479 341,342 376, 375 416, 417 474, 476 346, 344 377, 377 418, 418 475, 477 D/ese/Fue/s Ten tests in five laboratories for manual and for lutomatlo 375, 372 419, 424 515, 516 612, 613 355, 355 407, 407 507, 507 804, 601 366, 364 415, 417 511,511 607, 605

Max Min Average Max MIn Average

268, 268.5 264, 265 265.5, 268.5 341.5, 343 337, 338.5 340, 340,5

End Point (Final Boiling Point) 514, 515 507, 509 510, 512 647, 649 639, 641 644, 645

Max M~ Average Max Min Average

TABLE A1.3 Sample 1 2 3 4 5 6 7 8 9 10 11 12 13A 14A IBP +1.1 (+0.9) +0.7 +0.3 +0.5 +1.2 +0.3 +0.3 +1.7 +1.5 +0.9 +1.0 +0.3 +0.5 5~ +1.9 (0.0) +1.4 +0.6 +1.3 +1.2 +0.8 +0.5 +2.0 +1.6 +1.1 (+2.4) a +0.3 +0.4

Bias B e t w e e n Methods (ADA-Manual) C (Based on A v e r a g e s of ABTM and IP Data) 20S +1.6 +0.5 +1.0 +0.8 +1.3 +1.2 +0.7 +0.6 +1.5 +0.7 +0.8 +1.2 +0.3 +0.5 30"~ +1.4 +0.4 +0.8 +0.3 +1.2 +1.2 +0.8 +0.7 +1.5 +0.4 +0.7 +1.2 +0.2 +0.8 408 +0.7 +0.6 +0.6 +0.7 +1.0 +1.1 +0.8 +1.2 +1.5 +0.5 +0.6 +1.2 +0.9 +1.1 50~ +0.8 +0.2 +0.3 +0.5 +0.9 +0.8 +1.0 +1.2 +1.2 +0.9 +1.1 +1.2 +1.4 +1.7 60~ +0.7 +0.1 +0.1 +0.8 +0.6 +1.1 +1.5 +1.1 +0.9 +1.0 +1.0 +0.9 +1.0 +1.7 70~ +0.7 +0.1 +0.2 +1.1 +0.8 +1.2 +1.6 +1.3 +1.3 +1.4 +0.4 +1.1 +0.1 +1.0 80S 90~ 95~ FBP -0.4 (-1.2) n -0.8 -0.9 -0.8 -0.3 -0.7 -0.8 -1.2 -2.1 -0.8 -0.9 -1.2 -0.8 1 2 3 4 5 5 7 8 9 10 11 12 13A 14A +0.1 +0.4 +0.7 +0.4 (+4.7)a (+1.3)m +0.8 +0.5 +0.1 +1.2 +0.8 t-0.8 +1.0 +0.4 +0.4 +0.2 -0.1 +02 +1.6 +1.5 +1.7 +1.9 +1.1 +1.2 +0.8 -0.4 +0.4 +1.9 +0.9 +0.1 +0.5 -0.4 +0.1 +02 -0.7 (-0.8) I +1.1 +1.2 +1.0 +0.8 +0.3 0.0

10~; +2.2 +0.8 +1.6 +0.8 +1.3 +1.6 +0.8 +0.7 +1.8 +1.2 +1.2 +2.3 +0.4 +0.7

A (3esOI~s. a ( ) Points not Inolucled in the wedal(~ analysis. TABLE A1.4 Sample 1 2 3 4 5 6 7 8 9 10 11 12 13A 14A A euohols. IBP +1.9 (+1.6)m +1.2 +0.5 +0.9 +2.1 +0.6 +0.6 +3.1 +2.7 +1.6 +1.8 +0~ +0.9 5 +3.4 (0.0)a +2.5 +1.1 +2.3 +2.2 +1.4 +0.9 +3.5 +2.7 +2.0 (+4.2) m +0.5 +0.7 Bias B e t w e e n Methods (ADA-Manual) F (Based on A v e r a g e s of ASTM and IP Data) 10 "/, +4.0 +1.5 +2.8 +1.5 +2.3 +2.8 +1.4 +1.3 +3.2 +2.1 +2.1 +4.1 +0.7 +1.2 20 Ii +2.9 +0.9 +1.7 +1.4 +2.3 +22 +1.3 +1.0 +2.7 +1.2 +1.4 +2.1 +0.5 +0.9 30 I~ +2.5 +0.7 +1.4 +0.6 +2.1 +2.1 +1.5 +1.2 +2.6 +0.8 +1.2 +2.2 +0.3 +1.4 40 ~; +1.2 +1.1 +1.0 +1.2 +1.7 +2.0 +1 +2.1 +2.7 +1.0 +1.0 +2.1 +1.6 +2.0 50 ~ +1.4 +0.4 +0.5 +1.1 +1.5 +1.4 +1.8 +2.1 +2.1 +1.5 +1.9 +2.1 +2.5 +3.0 60 S +1 2 +0.2 +0.1 +1.4 +1.0 +2.0 +2.6 +2.0 +1.6 +1.7 +1.7 +1.6 +1.7 +3.0 70 S +1.3 +0.1 +0.4 +1.9 +1.4 +2.1 +2.8 +2.4 +2.3 +2.5 +0.8 +1.9 +0.2 +1.8 80 ~ +0.1 +0.7 +1.5 +2.1 +1.8 +0.4 +2.8 +3.4 +1.1 +3.4 +0.9 +0.4 +2.0 +1.5 90 ~ +0.8 (+8.4) s +0.9 +1.4 +0.7 -0.1 +2.6 +2.0 -0.7 +1.6 -0.7 -1.2 +2.1 +0.6 95 +1.2 (+2.3)m +0.1 +0.9 +0.8 +0.4 +3.1 +2.1 +0.8 +02 +02 (-1.5) a +1.8 0.0 FBP -0.7 (-2.2) B -1.4 -1.7 -1.7 -0.6 -1.3 -1.4 -2.1 -3.8 -1.4 -1.7 -2.2 -1.4 Sample 1 2 3 4 5 6 7 8 9 10 11 12 13a 14m

?4

D 86

APPENDIXES
(Nonmandatory Information)

XI. EXAMPLES

ILLUSTRATING

CALCULATIONS

FOR REPORTING

OF DATA

X I . I Thermometer Readings Corrected to 101.3 kPa (760 mm Hg) Pressure: X I . I . 1 Thermometer Readings Correction to 101.3 kPa (see 10.3): correction ('C) -- 0.0009 (101.3 - 98.6) (273 + to) ( X I . I ) correction ('F) = 0.00012 (760 - 740) (460 + ~). XI.1.2 Xl.I.3 (X 1.2) (XI.3) (XI.4)

X I . 2 . 2 Thermometer Reading at 50 % Evaporated (45.3 % Recovered) (See 10.8.1):


T ~ o ~ ' C ) = 9 4 + [(109 - 94)(45.3 - 40)/(50 - 40)]

- lo2.o'c (xi.7)
Tso~'F) 201 + [(228 201)(45.3 40)/(50 40)]

- 215.3"F

(XI.8)

Loss Correction to 101.3 kPa (see 10.5):


corrected loss = (0.750 x 4.7) + 0.125 = 3.6. corrected recovery 94.2 + (4.7 - 3.6) 95.3.

X 1.2.3 Thermometer Reading at 90 % Evaporated (85.3 % Recovered) (See 10.8.1): TgoE(*C) - 181.5
+ [(201.0 1 8 1 . 5 ) ( 8 5 . 3 - 8 5 ) / ( 9 0 - 85)] = 182.7"C (XI.9)

Recovery Correction to 101.3 kPa (see 10.5.2):


= =

X I.2 Thermometer Readings at Prescribed Percentages Evaporated: X 1.2.1 Thermometer Reading at 10 % Evaporated (5.3 % Recovered) (see 10.8.1): Tto~'C )
=

Tgo~('F) = 359 + [(394 - 359)(85.3 - 85)/(90 - 85)] - 361.1"F

(XI.10)

X 1 . 2 . 4 Thermometer Reading at 90 % Evaporated (85.3 % Recovered) Not Corrected to 101.3 kPa Pressure (See 10.8.1): T g o ~ ( ' C ) - 180.5
+ [(200.4 1 8 0 . 5 ) ( 8 5 . 3 - 8 5 ) / ( 9 0 - 85)] 181.7"C (XI.II)

33.5 + [(40.5

33.5)(5.3

5)/(10

5)] = 33.9"C

(XI.5) (XI.6)

Tlon('F) = 92 + [(104 - 92X5.3 - 5)/(10 - 5)] = 92.7"F

TgoE('F) = 357 + [(392 - 357X85.3 - 85)/(90 - 85)] - 359.1"F

(Xl.12)

TABLE X1.1 B,ewnetrk: Pm__~__~e

Thermometer Readings Corrected to 101.3 kPa (780 mm HO) Pressure


Observed 98.6 kPa (740 mm HO) oc OF 25.5 33.0 39.8 48.0 54.5 74.0 93.0 108.0 123.0 142.0 166.8 180.5 200.4 ii5.0
54.2

Coffered 101.3 kPa (780 mm HO) oC OF 26.0 88.8 40.0 48.8 55.0 75.0 94.0 109.0 124.0 143.5 155.0 181.6 201.0 ~)i(5
983

Init~ Boiling Point 6 ~ recovered 10 recovered 15 ~; recovered 20 ~t recovered 80 ~t recovered 40 ~ re(~)ver~ 50 ~t reoovemd 60 Y, reoovemd 70 ~ recovered 80 Y, reoovemd 85 Y, reoovemd 90 recovered 95 recovered End Point
z

78 91 133 115 133 165 199 228 253 255 332 357 392 4i9
.

79 92 104 116 131 187 201 228 258 290 3,34 359 394 ;'~i
..

Residue. Y,
Los,

1.1
4.7

...
...

1.1
3.8

...
...

75

~1~) D 86

X2. CALCULATION OF REPEATABILITY AND REPRODUCIBILITY OF VOLUME % (RECOVERED OR EVAPORATED) AT A PRESCRIBED TEMPERATURE READING X2.1 Some specifications require the reporting of the volume % evaporated or recovered at a prescribed temperature. The statistical determination of the precision of the volume % evaporated or recovered at a prescribed temperature has not been directly measured for Groups 0 or 1 in an interlaboratory program. The following procedure makes the assumption that the precision of the volume % evaporated or recovered at a prescribed temperature is equivalent to the precision of the temperature measurement at that point divided by the rate of change of temperature versus volume % evaporated or recovered. The estimation becomes less valid at high slope values. X2.2 Calculate the rate of change in thermometer reading in degrees Celsius (or Fahrenheit) per the volume % evaporated or recovered ( ' C ( F ) / V % ) in accordance with 11.4 using temperature values which are higher and lower than the prescribed temperature in question. X2.3 Calculate the repeatability (ro) or reproducibility of temperature (Ro) or both of the temperature using the value of " C ( F ) / V % as determined in X2.2 and the appropriate table or figure as indicated in Table AI.I. X2.4 Determine the repeatab'dity or reproducibility or both of the volume % evaporated or recovered at a prescribed temperature from the following formulas:
rVOI % == r J ( ' C ( F ) I V % )

TABLE X2.1 DiatlllatlonPoint Recovered,mL 10 20 30 40 DletBationPoint Evaporated, mL 10 20 30 40

Distillation Data From Group 1 Sample Manual Distillation Temperature, C 84 94 103 112 Temperature, C 83 94 103 111 Temperature, F 183 202 217 233 Temperatt~, F 182 201 217 232 Volume (mL) Recoveredat

93.8 (200) C (F)


18.0

voeme (rat.)
Evaporated at

93.a (2oo) "c (F)


18.4

'%ol % - RJ('C(F)/V%)

(X2.1)

where:
Wol % Rvol % = repeatability of the volume % evaporated or

X2.5 E x a m p l e Calculation: X2.5.1 For a Group 1 sample exhibiting distillation characteristics as per Table X2.1. To determine 'vol % evaporated at 93.YC (200"F) (from 11.4.5). "C/V %, F/V % - 0.05 (T(,+,o) C / V % , F / Y % - 0.05 (7"(,+,0) T(,-,0)) - 7"(,-,o9 "C/V% = 0.05 (Too) - TOo)) F / v ~ - 0.05 (Too) - 1"(,=) "C/V% = 0.05 (103 - 83) " F / V % - 0.05 (217 - 182) C l V % - 0 . 0 5 (20) "F/V% - 0.05 (35)
-

CIV%

= 1.0

F / V % = 1.75

recovered, =reproducibility of the volume % evaporated or recovered, ro = repeatabifity of the temperature at the prescribed temperature, Ro = reproducibility of the temperature at the prescribed temperature, and " C ( F ~ I V % = rate of change in thermometer reading in degrees Celsius (Fahrenheit) per the volume % evaporated or recovered.

X2.5.2 From Fig. 4 (C) or ro - 0.864 ( ' C / V % ) + 1.214 ro - 0.864 (1.0) + 1.214 re - 2.078 X2.5.3 From X2.4: 'vol % = r J ( ' C / V %)
"vol % = 2.078/I.0 "vol % = 2. I

Fig. 5 ('F): ro - 0.864 ( ' F / V ~ ) + 2.186 r o - 0.864 (1.75) + 2.186 r e " 3.698
rVOl % = r J ( ' F / V %) "vol % = 3.698/1.75 'vol% = 2.1

The Amerioan ~ for Tutlng and Material taku no poaltlon re~m=tlr~ the validity of any patant r l ~ aimfred In oonnectk~ with any Item mentioned In this Mandard. U~mraof thll Itandetd are exprmmly advlHd that detocn'dtmtlon of the validlly of any auch patent rights, end the risk of Infringement of auch rights, are entirely their own relponalblllty.
Thl8atandard le subject to revlalonat any time by the ruponalble teohnlcalcommittee and must be revlewed every llveyears and Ifnot revlsed,eitherr m ~ or withdrawn. Your comments are invitedeitherfor~ of alandard or foradditlonalBtandarda thla and eheuld be a d d ~ to A S T M Headquarter. Your comments willreceive carefuloonalderatlonat a meetlng of the re~oo~Ible teohnlcal aynmittee. which you may attend. Ifyou feel that your comments have not ~ falrhearing you should make your a views known to the ASTM Comm~ee on Standard& 100 Barr Harbor Drive, West Conshehockon, PA 19428.

76

( 1 ~ ) Designation: D 87 - 87 (Reapproved 1993) (1

Designation:5583
m t,t~m ~uM

An AmericanNational Standard Technical Assoc~ti0t~of Pulp and PlkowIndulW Standard MethodT 630 m-61 Method 1462-FecW'alTest Method Standard No. 791b Brim Standard 4695

Standard Test Method for Melting Point of Petroleum Wax (Cooling Curve) 1
This standard is issued under the fixed designation D 87; the number immediately following the designation indicates the year of original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A superscript e~ilon (() indicates an editorial change since the last revision or reapproval.
This test method was adopted as a joint ASTM-IP standard in 1966.

~' NoTE--Keywords were added editorially in October 1993.

1. Scope 1.1 This test method covers the determination of the melting point (cooling curve) of petroleum wax. It is unsuitable for waxes of the petrolatum group, microcrystalline waxes, or blends of such waxes with paraffin wax or scale wax.
NOTE I - - F o r additional m e t h o d s used for testing petroleum waxes, see Test Method D 127 and Test Method D 938. Results m a y differ, depending on the m e t h o d used. For pharmaceutical petrolatum, Test M e t h o d D 127 usually is used.

4. Summary of Test Method

4.1 A specimen of molten wax in a test tube fitted with a thermometer is placed in an air bath, which in turn is surrounded by a water bath held at 16 to 28"C (60 to 80"1='). As the molten wax cools, periodic readings of its temperature are taken. When solidification of the wax occurs, the rate of temperature decreases, yielding a plateau in the cooling curve. The temperature at that point is recorded as the melting point (cooling curve) of the sample.
5. Significance and Use

1.2 The values stated in SI units are to be regarded as the standard. The values in parentheses are for information only. 1.3 This standard does not purport to address all of the

safety problems, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applica. bility of regulatory limitations prior to use.
2. Referenced Documents

2. I A S T M Standard:
D 127 Test Method for Drop Melting Point of Petroleum Wax, Including Petrolatum2 D 938 Test Method for Congealing Point of Petroleum Waxes, Including Petrolatum2 E 1 Specification for ASTM Thermometers3
3. Definition

5.1 Melting point (cooling curve) is a test that is widely used by wax suppliers and consumers, it is particularly applied to petroleum waxes that are rather highly paraffinic or crystalline in nature. A plateau occurs with specimens containing appreciable amounts of hydrocarbons that crystallize at the same temperature, giving up heat of fusion, thus temporarily retarding the cooling rate. In general, petroleum waxes with large amounts of non-normal hydrocarbons or with amorphous solid forms will not show the plateau.
6. Apparatus

6.1 The necessary apparatus is described in Annex A 1.


7. Test Specimen

3.1 melting point (cooling curve) of petroleum wax-temperature at which melted petroleum wax first shows a minimum rate of temperature change when allowed to cool under prescribed conditions. NOTE 2--The so-called "American Melting Point" is arbitrarily 1.65"C (3F) above the Melting Point (Cooling Curve) of Petroleum
Wax.

7.1 Obtain a sample ofwax representative of the shipment to be tested. From each test unit obtain a portion of wax weighing at least 25 g for each melting point determination. 8. Procedure 8.1 Support the air bath in its proper position in the water bath. Fill the water bath to within 13 mm (I/2 in.) of the top with water at a temperature of 16 to 28"C (60 to 80"F). The bath temperature is kept within these limits throughout the test. 8.2 Heat the wax sample to at least 8"C (15"F) above its expected melting point (see Note 3). To heat the wax sample use a suitable container in an oven or water bath which is held at a temperature not exceeding 9YC (200"F). Avoid the use of direct heat such as flame or hot plate. Do not keep the sample in the molten state longer than l h. NOTE 3--If no estimate of the melting point is available, heat the wax sample to 10"C (15F) above the temperature at which the wax is 77

' This test method is under the jurisdiction of ASTM Committee D-2 on Petroleum Products and Lubricants and is the direct responsibility of Subcom, mitte D02.10 on Properties of Petroleum Wax. In the IP, this test method is under the jurisdiction of the Standardization Committee. Current edition approved Oct. 30, 1987. Published December 1987, Originally published as D 87 - 21 T. Last previous edition D 87 - 77 (1982). 2 Annual Book of ASTM Standards, Vol 05.01. 3 Annual Bcu)k of ASTM Standards, Vols 05.03 and 14.03.

~) D 87
completely molten, or to from 90 to 93"C (195 to 200"F) before proceeding to the next step. 8.3 Fill the test tube to a height of 51 mm (2 in.) with the melted sample. Insert the melting point thermometer through the center of a cork so that the 79-mm (Y/g-in.) immersion line is at the lower surface of the cork. Insert the cork into the test tube so that the bottom of the thermometer bulb is 10 mm (3/s in.) from the bottom of the test tube. Support the test tube assembly in the air bath as shown in Fig. 1 while the temperature of the molten wax is still at least 8C (15F) above its expected melting point (Note 3). 8.4 Read the melting point thermometer every 15 s. Record each reading to the nearest estimated 0.05"C (0.1 F). Observe the progress of these sequential readings to determine the appearance of the plateau. Identify the plateau as the first five consecutive readings all of which agree within 0. IC (0.2F). Discontinue the test after obtaining these five plateau readings. NOTE 4mlf no plateau appears as defined above, the reading procedure is continued until either (1) the temperature reached 38"C (100"F) or (2) the temperature reaches a point 8"{=(15"F) below a temperature where the wax has solidified(as may be observed through a transparent bath). In either of these cases the test is discontinuedand the method is judged Not Applicable to the sample (see Note I for other methods).

9. Calculation and Report 9.1 Average the first five consecutive thermometer readings of the identified plateau, which agree within 0.1"C (0.2F). Correct this average for error in the thermometer scale where necessary. 9.2 Report the result to the nearest 0.05C (0. l'F) as the Petroleum Wax Melting Point (Cooling Curve), Test Method D 87.

10. Precision and Bias 10.1 Precision--The precision of this test method as determined by statistical examination of inteflaboratory results is as follows: NOTE 5--This method is considered suitable for waxes of melting point between 38"C(100"F) and 82"C(180"F). The precisiondata below were obtainedin interlaboratorystudiesby ASTM CommitteeD-2 using waxes in 127 to 144"F range and by IP using waxes in 108 to 151"F range. 10.1.1 Repeatability--Tbe difference between two test results, obtained by the same operator with the same apparatus under constant operating conditions on identical test material, would in the long run, in the normal and correct operation of the test method, exceed the following values only in one case in twenty: 0. I'C (I.0"F) 10.1.2 Reproducibility---The difference between two single and independent results obtained by different operators working in different laboratories on identical test material would, in the long run, in the normal and correct operation of the test method, exceed the following values only in one case in twenty: 0.5"C ( 1.0"1=) 10.2 These precision values have been obtained by statistical examination of interlaboratory test results and were first published in 1965. These values are based on a study among 15 laboratories, using five paraffin waxes with a melting point range of 53 to 66C (128 to 151F). 10.3 Bias--The procedure in this test method for has no bias because the value of melting point can be defined only in terms of a test method.
11. Keywords 11.1 cooling curve; melting point; petroleum wax; wax

78

D87

ANNEX

(Mandatory Information)
A1. APPARATUS AI. 1 Test Tube--A standard glass test tube, 25 mm (1 in.) in outside diameter, and 100 mm (4 in.) in length. It may be marked with a reference line for sample filling at 51 mm (2 in.) above the bottom, and a reference line for positioning of the bottom oftbe thermometer at 10 mm (3/s in.) above the bottom. AI.2 Air Bath--A cylinder 51 mm (2 in.) in inside diameter and 114 mm (4'/2 in.) in depth. Provide the air bath with a tightly fitting cork having a central opening for holding the test tube firmly in a vertical position in the center of the air bath. A1.3 Water Bath--A suitable cylindrical vessel, 130 mm (51/s in.) in inside diameter and 152 mm (6 in.) in depth. Provide a fitted cover equipped to support the air bath vertically so that the sides and bottom of the air bath are surrounded by a layer of water 38 mm (1'/2 in.) thick. Provide the cover with an opening through which the bath thermometer may be suspended 19 mm (3/4in.) from the outside wall of the water bath.
NOT~ A l . l - - T h e air bath, water bath, and water bath cover may be

i ;nLLINL E ~ I N
"-'l-

made in one assemblyas shown in Fig. AI.I. AI.4 Melting Point Thermometer--A Wax Melting Point Thermometer having the range shown below and conforming to the requirements as prescribed in Specification E 1 or in the specifications for IP thermometers:
Thermometer Number

Temperature Range
(Sll

ASTM 14C 14F

lP 17C 17F

38 to 82"C 100 to 180"F

NoTE--Dimensionsin inches(milUmetres). FIG. A1.1 Apparatus for Determination of Melting Point (Cooling Curve) of Petroleum Wax

A 1.5 Bath Thermometer--Any suitable partial immersion thermometer, accurate to 1.0"C (2"F) throughout the required range. AI.6 Timer--Interval timer or stop watch.

The American Society for Tasting and Materials takes no position respecting the validity of any patent rights asserted in connection with any item mentioned in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk of infringement of such rights, are entirely their own responsibility. This standard is subject to revision at any time by the responsible technicet committee and must be reviewed every five years and if not revised, either raspproved or withdrawn. YOurcomments are invited either for revision of this standard or for additional standards and should be addressed to ASTM Headquarters. YOurcomments will receive careful consideration at a meeting of the responsible technical committee, which you may attend, if you feel that your comments have not received a fair hearing you should make your views known to the ASTM Committee on Standards, 1916 Race St., Philadelphia, PA 19103.

79

(]~l~ Designation: D 96-88 (Reapproved 1994)~1


~ I) Designation: MPMS Chapter 10.4

An American National Standard Bntish Standard 4385 American Association State Htghway Transportation Standard AASHTO No. 3"55

Standard Test Method for Water and Sediment in Crude Oil by Centrifuge Method (Field Procedure) 1
This standard is issued under the fixed designation D 96; the number immediately following the designation indicates the year of original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A superscript cpsilon (~) indicates an editorial change since the last revision or re.approval.

This method has been approved by the sponsoring committees and accepted by the Cooperating Societies in accordance with established procedttres. This test method has been adopted for use by government agencies to replace Method 3003 of Federal Test Method Standard No. 791b. Annex A 1 is under revision and will be included in subsequent revisions to this standard.
o NOTE--Section 11 was added editorially in May 1994.

1. Scope 1.1 This test method covers the centrifuge method for determining sediment and water in crude oil during field custody transfers. This test method may not always provide the most accurate results, but it is considered the most practical method for field determination of sediment and water. When a higher degree of accuracy is required, the laboratory procedure described in Test Methods D 4006, D 4377 or D 473 should be used.
NOTE l - - W a t e r by distillation a n d sediment by extraction are considered the most accurate m e t h o d s o f d e t e r m i n i n g sediment and water in crude oils. As such, these m e t h o d s s h o u l d be employed to resolve differences in results from variations o f this procedure or between this procedure a n d other methods, or in the case o f a dispute between parties.

D 3699 Specification for Kerosine4 D 4006 Test Method for Water in Crude Oil by Distillation 4 D 4057 Practice for Manual Sampling of Petroleum and Petroleum Products 4 D4177 Practice for Automatic Sampling of Petroleum and Petroleum Products 4 D4377 Test Method for Water in Crude Oils by Potentiometric Karl Fischer Titration 4 E 1 Specification for ASTM Thermometers 5 E 542 Practice for Calibration of Volumetric Ware 6 2.2 AP1 Standards: 7

Manual of Petroleum Measurement Standards Chapter 8, Sampling Petroleum and Petroleum Products Chapter 10, Sediment and Water

1.2 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

3. Summaryof Test Method


3.1 Known volumes of crude oil and solvent (water saturated if required) are placed in a centrifuge tube and heated to 60"C + 3"C (140*F _+ 5*F). After centrifugation, the volume of the sediment-and-water layer at the bottom of the tube is read. NOTE 2--It has been observed that for some waxy crude oils, temperatures of 71"C(160F) or higher may be required to melt the wax crystals completely so that they are not measured as sediment. If temperatures higher than 60"(2 (140"1 ) are necessary to eliminate this =. problem, they may be used with the consent of the parties involved. If water saturation of the solvent is required, it must be done at the same temperature.

2. ReferencedDocuments
2. I A S T M Standards:
D 235 Specification for Mineral Spirits (Petroleum Spirits) (Hydrocarbon Drycleaning Spirits)2 D 362 Specification for Industrial Grade Toluene 2 D 473 Test Method for Sediment in Crude Oils and Fuel Oils by the Extraction Method 3 D 846 Specification for Ten-Degree Xylene 2 D 1209 Test Method for Color of Clear Liquids (PlatinumCobalt Scale)2
This test method is under the jurisdiction of Committee D-2 on Petroleum Products and Lubricants and is the direct responsibility of Subcommittee D02.02.OB on Sediment and Water (Joint ASTMdP). Current edition approved March 25, 1988. Published December 1988. Originally published as D 96 - 63T. Last previous edition D 96 - 73 (1984). ~l 2 Annual Book of ASTM Standards, Vol 06.04. 3 Annual B~)k of ASTM Standards, Vol 05.01.

4. Significanceand Use
4.1 A determination of sediment and water content is required to determine accurately the net volumes of crude oil involved in sales, taxation, exchanges, inventories, and
4 Annual Book of ASTM Standards, Vol 05.02. Annual Book of ASTM Standards, Vol 14.03. 6 Annual Book of ASTM Standards, Vol 14.02. 7Available from American Petroleum Institute, 1220 L St., Northwest, Washington, DC 20005.

80

q~ D 96
TABLE 1 Rotation Speeds Necessary to Produce a Relative Centrifugal Force of 500 for Centrifuges of Various Diameters of Swing Diameter of SwingA Millimeters Inches 305 330 356 381 406 432 457 483 508 533 559 584 610 12 13 14 15 16 17 18 19 20 21 22 23 24 Rotation Speed (r/min) 1710 1640 1580 1530 1480 1440 1400 1360 1325 1290 1260 1240 1210 TABLE 2 Minimum Graduation Requirements and Maximum Calibration Tolerances for 203-ram (8-in.) Cone-Shaped Tubes Range, mL 0-0.1 >0.1-0.3 >0,3--0,5 >0.5-1.0 >1.0-2.0 >2.0-3.0 >3.0-5.0 >5.0-10 >1 0-25 >25-100 Subdivision, mL 0.05 0.05 0.05 0.10 0.10 0.20 0.5 1 5 25 Volume Tolerance. mL +0.02 +0.03 +0.05 0.05 +0.10 0.10 0.20 -0.50 +1.00 1.00

A Measured between the tips of the opposite tubes when lhe tubes are in

TABLE 3 Minimum Graduation Requirements and Maximum Calibration Tolerancea for 167-mm (6-in.) Cone-Shaped Tubes Range, mL >O-0.1 >0.1-0.3 >0.3-0.5 >0.5-1.0 >1,0-1.5 >1.5-2.0 >2.0-3.0 >3.0-5.0 >5.0-10 >10-25 >25-103 A Graduations at 50 anti 100. Subdivision, mL 0.05 0.05 0.05 0.10 0.10 0.10 0.20 0.50 1 5 ~ Volume Tolerance, mL +0.02 +0.03 +0.05 +0.07 0.10 +0.20 :L-0.30 0.50 +0.75 +1.0 +1.5

rotat~ posroon.

custody transfers. An excessive amount of sediment and water in crude oil is significant because it can cause corrosion of equipment and problems in processing and transporting and may violate federal, state, or municipal regulations.
5. Apparatus

5.1 Centrifuge--A centrifuge shall be capable of spinning two or more centrifuge tubes at a speed that can be controlled to give a minimum relative centrifugal force of 500 at the tip of the tubes. The rotation speed necessary to produce a relative centrifugal force of 500 for various diameters of swing can be determined from Table 1 or from one of the following equations: r/min ffi 1335 J - ~ (l) r/rain ffi 265 v r ~ (2) where: rgm = rotation speed, in revolutions per minute. rcf = relative centrifugal force, d = diameter of swing, in mm (Eel 1) or in. (Eq 2), measured between the tips of opposite tubes when the tubes are in their rotating position. The revolving head, trunnion rings, and trunnion cups, including the cushions, shall be constructed to withstand the maximum centrifugal force capable of being delivered by the power source. The trunnion cups and cushions shall firmly support the tubes when the centrifuge is in motion. The centrifuge shall be enclosed by a metal shield or case strong enough to contain flying debris in the event a tube breaks or the centrifuge malfunctions. 5.1.1 The centrifuge shall be heated and shall be capable of maintaining the sample at a temperature of 60C +_ 3C (140F _+ 5F). The minimum allowable temperature in the field shall be 52"C (125F). 5.2 Centrifuge Tubes: 5.2.1 Centrifuge tubes shall be cone shaped and 203 mm (8 in.) or 167 mm (6 in.) in length. Tubes shall conform to the dimensions given in Fig. I (203 ram) or Fig. 2 (167 mm) and shall be made of thoroughly annealed glass. A 200-part tube shall conform to the dimensions shown in Fig. 2, with the marking for each division multiplied by 2 (for example, 25 mL = 50 parts). The mouth of each tube shall be constricted for closure with a stopper. Graduations for the
81

203-mm (8-in.) and 167-mm (6-in.) tubes shall be in accordance with the requirements of Tables 2 and 3, respectively. The scale errors for a centrifuge tube shall not exceed the tolerances specified in Tables 2 and 3. The graduation requirements and scale-error tolerances shown in Tables 2 and 3 apply to calibrations made by reading the bottom of the shaded meniscus of air-free water at a temperature of 20"C (68"F). The graduations on each tube shall be clearly numbered as shown in Figs. I and 2. 5.2.2 The tube graduation marks' accuracy shall be volumetrically verified or gravimetrically certified before field use of the tube, in accordance with Practice E 542 using National Institute of Standards and Technology-traceable equipment. The verification or certification shall include a calibration check at each mark up through the 0.5-mL (l-part) mark; at the 1-, 1.5-, and 2-mL (2-, 3-, and 4-part) marks: and at the 50- and 100.mL (100- and 200-part) marks. The tube shall not be used ff the scale error at any mark exceeds the applicable tolerance from Table 2 or 3. 5.3 Preheater--The preheater shall be either a metal block or a liquid bath of sufficient depth to permit immersion of the centrifuge tube in the vertical position to the 100-mL litre (200.part) mark and capable of heating the sample to 60"C + 3"C (140F + 5F). 5.4 Thermometer shall have graduations at intervals of IC (2"F) or less and shall be accurate to + I'C (+2"F). A thermometer such as ASTM IC or IF is suitable as shown in Specification E 1.
6. Reagents

6.1 The reagents listed in this section are satisfactory for use in field testing. 6.2 Demulsifier--When necessary, a demulsifier should

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D96
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FIG. 2 Cone-Shaped Centrifuge Tube, 167 mm (6 in.)

Line of inside bottom INSIDE TAPER SHAPE FIG. 1 Cone-Shaped Centrifuge Tube, 203 mm (8 in.)

be used to promote the separation of water from the sample, to prevent water from the sample, clinging to the walls of the centrifuge tube, and to enhance the distinctiveness of the water-oil interface. In some eases a demulsifier is required to attain agreement with the base method (see Note 1). When a demulsifier is used, it should be mixed according to the manufacturer's recommendations and should never add to the volume of sediment and water determined. The demulsifier should always be used in the form of a demulsifier-solvent stock solution or be premixed with the solvent to be used in the test. 6.3 Kerosine (Specification D 3699) 6.3.1 The typical characteristics of kerosine are a distillation range of 205-300"C (401-572"F), a maximum freezing point of -30"C (-22"F), and a minimum flash point of 38"C (100"F). 6.3.2 Stoddard solvent and kerosine do not have to be
82

saturated with water, since the solubility of water in these solvents is not significant at 60C (140F). NOTe 3: Warning--Kerosine is combustible(See Annex AI.I). 6.4 Stoddard Solvent (Specification D 235): 6.4.1 The typical characteristics of Stoddard solvent are a distillation range of 149-208"C (300--407"F), a minimum flash point of 38"C (100*F), and aromatics plus olefins content of less than 20 % by volume.
NOTI~ 4: Warning--Stoddard solvent is combustible (See Annex

AI.2). 6.4.2 See 6.3.2. 6.5 Toluene (Specification D 362): 6.5.1 The typical characteristics of toluene are a molecular weight of 92, an American Public Health Association (APHA) color of 10 (per D 1209), a boiling range (initial to dry point) of 2.0"C (3.6"F) [recorded boiling point of I 10.6"C (231.1"F)], and 0.001% residue after evaporation. Toluene passes the American Chemical Society (ACS) test for substances darkened by H2SO4.
NOTE 5: Warning--Toluene is flammable (See Annex A1.3).

6.5.2 Toluene and xylene shall be saturated with water at 60*C + 3"C (140F + 5*F) and maintained at this tempera-

~
ture until used. A procedure for the saturation of solvents is given in the appendix. The water-saturated solvent shall be free from suspended water at the time of use. Toluene and xylene are recommended for sediment-and-water determinations involving asphaltenic crude oils. 6.6 Xylene (Specification D 846): 6.6.1 The typical characteristics of xylene are a molecular weight of 106, an APHA color of not more than 10 (in accordance with Test Method D 1209), a boiling range of 137 to 144"C (279 to 291"F), and 0.002 % residue after evaporation. Xylene passes the ACS test for substances darkened by sulfuric acid.
NOTE 6: Warning--Xylene is flammable (See Annex AI.4).

D96
8.4 Place the tubes in the trunnion cups on opposite sides of the centrifuge to establish a balanced condition. Retighten the stoppers and spin for at least 5 minutes at a minimum relative centrifugal force of 500. 8.5 Immediately after the centrifuge comes to rest, verify the temperature. Do not disturb the oil-water interface with the thermometer. The test is invalid if the final temperature after centrifugation is below 52"C (125"F).
NOTE 8mlf the final temperature is found to be below 52C (125"F), adjust the centrifuge heater to increase the final test temperature and reinitiate the procedure, beginning with 8.2.

6.6.2 See 6.5.2. 7. Sampling 7. I Sampling is defined as all steps required to obtain a representative quantity of the contents of any pipeline, tank, or other system and to place it in an appropriate centrifuge tube. 7.2 The sample shall be thoroughly representative of the crude oil in question, and the portion of the sample used for the sediment and water determination shall be thoroughly representative of the sample itself. If an automatic custody transfer (LACT) unit is involved, vigorous agitation of the sample container is required before the sample is transferred to the centrifuge tube or tubes. Only representative samples obtained as specified in Practices D 4057 or D 4177 shall be used for this test method. 8. Procedure 8.1 Fill each of two centrifuge tubes to exactly the 50-mL (100-part) mark with a sample taken directly from the sampling device (for example, a thief bottle, beaker, or LACT sample container) or the container in which the sample was collected. Then fill each tube with solvent to exactly the 100-mL (200-part) mark. Read the top of the meniscus at both the 50- and 100-mL (100- and 200-part) marks. If experience indicates that a demulsifier is required and one has not already been added to the solvent, add to each tube quantity of demulsifier-solvent stock solution that has previously been determined to be satisfactory for the crude oil under test. Stopper each tube tightly and invert the tubes a minimum of l0 times to ensure that the oil and solvent are uniformly mixed.
NOTE 7: Caution--In general, the vapor pressures of hydrocarbons at 60"C (140F) are approximately double those at 40"C (104F). Consequently, tubes should always be inverted at a position below eye level.

8.5.1 Read and record the combined volume of sediment and water at the bottom of each tube as indicated in Table 4 and Fig. 3 (Table 5 and Fig. 4 for 200-part tubes). Reheat both tubes to 60"C 3"C (140*F ___ 5*F), return the tubes without agitation to the centrifuge, and spin for another 5 rain at the same rate. Repeat this operation until two consecutive consistent readings are obtained on each tube. 8.6 For the test to be considered valid, a clear interface must be observed between the oil layer and the separated water. No identifiable layering (that is, an emulsion) should be present immediately above the oil-water interface. In such cases, one or more of the following remedies may be effective: 8.6. I Shake the mixture between whirlings in the centrifuge just enough to disperse the emulsion. 8.6.2 Use a different or an increased amount of demulsifier. (The demulsifier should not, however, contribute to the volume of sediment and water.) 8.6.3 Use a different or an increased amount of solvent. After a satisfactory procedure for a particular type of oil has been worked out, it will ordinarily be suitable for all samples of the same crude oil. 9. Calculation and Report 9. I Compare the readings of the two tubes. If the difference between the two readings is greater than one subdivision on the centrifuge tube (see Table 2 or 3) or 0.025 mL (0.05 % for 200-part tubes) for readings of 0.10 mL (0.20 % for 200-part tubes) and below, the readings arc inadmissible and the determination shall be repeated. 9.2 If tubes graduated in 100 mL have been used for the determination, record the sum of the final volumes of sediment and water in each tube obtained, as specified in Section 8, and report this sum as the percentage of sediment and water (see Fig. 3 for reading and reporting sediment and water when using 100-mL cone-shaped centrifuge tubes). Report the results as shown in Table 6. 9.3 If direct-reading 200-part tubes have been used for the determination, the percentage of sediment and water is the average, to three decimal places, of the values read directly from the two tubes. The percentage can only be read directly from a 200-part tube if the tube contains 50 mL or 100 parts of oil.
TABLE 4 Procedure for Reading a 100-mL Cone-Shaped Tube
Read to Nearest, mL 0.0-0.2 0.2-1.0 >1.0

8.1.1 Where the crude oil is very viscous and mixing of the solvent with the oil is difficult, the solvent may be added to the centrifuge tube prior to the oil to facilitate mixing. In this case, extreme care must be taken to fill the centrifuge tube to exactly the 50-mL (100-part) mark with solvent and then to exactly the 100-mL (200-part) mark with the sample. 8.2 Loosen the stoppers to prevent pressure buildup during heating and immerse the tubes to the 100-mL (200-part) mark in a preheater. Heat the contents to 60"C __. 3"C (140*F 5*F). 8.3 Secure the stoppers and again invert the tubes 10 times to ensure uniform mixing of the oil and solvent. 83

Volume of Sedimentand Water, mL

0.025 0.05 0.10

D 96
TABLE 5 Procedure for Reading a 200-Part Cone-Shaped Tube Read to Nearest, % 0.05 0.10 0.20 0.O-0.4 0.4-2.0 >2.0 Tube I None visible None visible 0.025 0.025 0.05 0.05 0.075 0.075 0.10 0.10 TABLE 6 Expression of Results Tube 2 Trace 0.025 0.025 0.05 0.05 0.075 0.075 0.10 0.10 0.15 Total Sediment and Water, % 0 0.025 0.5 0.075 0.10 0.125 0.15 0.175 0.20 0.25 Volume of Sedimentand Water, mL

Volume of Sediment and Water, ~0

9.4 If the volume of oil is greater or less than 50 mL, or 100 parts, calculate the percentage of sediment and water as follows: Sediment and water, percent = (S/V) x 100 where: S -- volume of sediment and water, mL or parts and V = volume of oil tested, mL or parts. For example, if the total volume of oil tested (V) is 20 mL and the volume of sediment and water (S) is 0.15 mL: Sediment and water, % = (0.15/20) x 100 = 0.75 9.5 If the test conditions outlined in Section 6 are not followed exactly, the following must also be reported: 9.5.1 The solvent used and the water saturation temperature. 9.5.2 The type and amount of demulsifier (if used). 9.5.3 The temperatures of the sample and solvent, the

preheater temperature, the centrifuge temperature, and the temperature of the final mixture after centrifuging. 9.5.4. The number of samples or tubes used in the determination. 10. Precision and Bias 10.1 Precision--The precision of this test method is being determined.

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Procedure for Reading Sediment and Water When Using a Tube Reading in 100 mL

FIG. 4

Procedure for Reading Sediment and Water When Using a Tube Reading in 200 Parts

84

~
10.2 BiasmSince there is no accepted reference material suitable for determining the bias, no statement about bias is being made.

D96
11. Keywords 11.1 centrifuge; centrifuge tube; crude oil; field procedure; sampling; sediment and water; solvent

ANNEX

(Mandatory Information) A1. Precautionary Statements


AI.I Kerosine--Keep away from heat, sparks, or open flame. Keep container closed when not in use. Kerosine's vapor is harmful. Provide adequate ventilation when kerosine is used. Neither an Occupational Safety and Health Administration permissible exposure limit nor an American Conference of Governmental Industrial Hygienists threshold limit value has been established for kerosine. Ingestion of kerosine may cause irritation of the digestive tract; ingestion of large amounts may cause signs of central nervous system depression. Aspiration of this material into the nervous system depression. Repetitive applications of kerosine directly to the skin of laboratory animals over their lifetimes has resulted in skin cancer in the animals. Petroleum hydrocarbons of similar composition and boiling range have been shown to produce kindey damage and tumors in laboratory animals. Avoid skin contact with kerosine. Prolonged or repeated skin contact may cause defatting and drying of the skin. A I.2 Stoddard Solvent--Keep away from heat, sparks, or open flame. Its container should be kept closed when not in use. The solvent's vapor is harmful. Adequate ventilation should be provided when the solvent is used, and airborne concentrations should be kept below the established exposure limits. The permissible exposure limit established by the Occupational Safety and Health Administration for Stoddard solvent is 500 parts/million.The American Conference of Governmental IndustrialHygienists has establisheda threshold limitvalue of I00 parts per million. Inhalation of vapors or spray mist should be avoided. Acute overexposure may result in irritation of the throat and lungs. High concentrations may cause central nervous system depression. Aspiration of thismaterialinto the lungs may cause chemical pneumonia. Long-term exposure can cause chronic health effects.Chronic overexposure has resulted in liver,heart, and blood disorders. Intense and protracted exposure to the solvent may be associated with an increased risk of kidney cancer, kidney disease, and nerve and brain damage. Avoid skin contact with the solvent. Prolonged or repeated contact with the liquid can resultin drying and defatting of the skin that may result in irritationand dermatitis. AI.3 Toluene--Keep away from heat, sparks, or open flame. Keep container closed when not in use. Toluene's vapor is harmful. Provide adequate ventilation when toluene is used, and airborne concentrations should be kept below the established exposure limits. The Occupational Safety and Health Administrator has established a permissible exposure limit of 200 parts/million, with an acceptable ceiling of 300 parts/million and an acceptable maximum peak of 500 parts/million for 10 min. The American Conference of Governmental Industrial Hygienists has established a threshold limit value of 100 parts/million, with a short-term exposure limit of 150 parts/million for 1 min. Prolonged overexposure through inhalation may cause coughing, shortness of breath, dizziness and intoxication. Aspiration of this material into the lungs may cause chemical pneumonia. Long-term exposure to this material may cause chronic health effects. Toluene may remove fats from the skin and cause chronic dermatitis. Other potential hazards include possible liver, kidney, and nervous system damage and cardiac sensitization to epinephrine. In addition, toluene has been shown to be toxic to the embryo and fetus at high concentrations in animal experiments, however, such studies have failed to demonstrate frank birth defects. Prolonged or repeated skin contact may cause skin to become dry or cracked. AI.4 Xylene--Keep away from heat, sparks, or open flame. Keep container closed when not in use. Xylene's vapor is harmful. Provide adequate ventilation when xylene is used, and keep airborne concentrations below established exposure limits. The Occupational Safety and Health Administration's permissible exposure limit for xylene is 100 parts/million. The American Conference of Governmental Industrial Hygienists has established a threshold limit value of 100 parts/million with a 15-min short-term exposure limit of 150 parts/million. Overexposure through inhalation may cause shortness of breath, dizziness, intoxication, and collapse. Aspiration of this material into the lungs may cause chemical pneumonia. Long-term exposure to this material can cause chronic health effects. Prolonged, repeated exposure to high levels of xylene can induce central nervous system problems and may cause liver and kidney damage. Avoid prolonged or repeated skin contact with xylene. Skin contact may result in delayed skin irritation and blistering.

85

~) D 96

APPENDIX

(NonmandatoryInformation)
X1. DEMUI.~IFIERS AND WATER SATURATION OF SOLVENTS XI. I Water Saturation of Solvents: X I.I.I Fill each of two centrifuge tubes to the 2-mL (4-part) mark with water and then to the 100-mL (200-part) mark with the solvent to be saturated. X I. 1.2 Stopper the tubes and shake vigorously for 30 s, holding the tubes below eye level, to disperse the water in the solvent. Loosen the stoppers. X1.1.3 Place the tubes containing the water/solvent mixture into a sample preheater or heated (nonspinning) centrifuge maintained at a temperature of 60"C (140*F) for a minimum of 30 min. Xl.l.4 Inspect the water/solvent mixture for suspended water droplets before use. If any suspended water is visible, the tubes must be centrifuged at a temperature of 60"C (140*F) for 5 rain at a speed sufficient to give a relative centrifugal force of 500 at the tube tip. X1.1.5 Use the top 50 mL (100 parts) of the mixture from each tube for test purposes. Take particular care not to pour any of the free water in the tip of each tube into the sample. X 1.2 Demulsifiers: X 1.2.1 Although a good commercial crude-oil demulsifier will work effectively with a wide range of crude oils, there are some etudes for which one demulsifier is more effective than another. If the selected demulsifier does not provide the desired results, others should be tried. XI.2.20vertreatment with a demulsifier can add erroneously to the apparent sediment and water level. Demulsifiers do not in general contain water, but they do have a limited solubility in the solvent-sample and, if added in excessive quantities, can show up after centrifuging as a separate immiscible component at the bottom of the tube. To prevent this problem, the demulsifier should always be used in the form of a demulsifier-solvent stock solution or should be premixed with the solvent to be used in the test. In either case, the quantity of demulsifier to be added to the solvent should be based on tests for the particular demulsifier solvent combination. The demulsifier manufacturer's instructions should be followed when a demulsifier solution is prepared. X1.3 Demuisiliers and demulsifier-solvent solutions should always be stored in accordance with the manufacturer's recommendations. Each container used to store a demulsifier or demulsifier-solvent solution should be dated, and the contents should be discarded when they reach the demulsifier manufacturer's recommended shelf life.

The American Society for Testing and Materials takes no postt~on respecting the vahdity of any patent rights asserted in connection with any/tern mentioned in this standard. Users of this standard are expressly advised that determination of the vahdlty of any such patent rights, and the risk of mfringement of such rights, are entirely their own responsibility. This standard is subject to revision at any time by the responsible technical committee and must be reviewed every hve years and ff not revised, either reapproved or withdrawn Your comments are tnwted either for revision of this standard or for additional standards and should be addressed to ASTM Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical committee, whtch you may attend, if you feel that your comments have not received a fair hearing you should make your views known to the ASTM Committee on Standards, 100 Barr Harbor Drive, West Conshohocken, PA 19428,

86

q~)

Designation: D 97 - 96a

IPW Designation: 15/95


rHt I~lTur~

Standard Test Method for Pour Point of Petroleum Products I


This standard is issued under the fixed desit~mtion D 97; the number immediately following the d ~ a f i o n indicates the year of originaladoption or, in the case of revision,the year of lustrevision.A number in parenthesesindicatesthe year oflastreapproval.A superscript cpsilon (d indicates an editorialchan~ since the last rcvi~on or rcapproval.

This testmethod has been adoptedfor use by government agencies to replaceMethod 201 of Federal Test Method Standard No. 791b, and Method 4452 of Federal Test Method Standard No. 141.4. This test method was adopted as a joint ASTM-IP Standard in 1965.

1. Scope 1.1 This test method is intended for use on any petroleum product, a A procedure suitable for black specimens, cylinder stock, and nondistillate fuel oil is described in 7.8. A procedure for testing the fluidity of a residual fuel oil at a specified temperature is described in the appendix. 1.2 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific hazard statements, see Section 6. 2. Referenced Documents 2.1 A S T M Standards: D 117 Guide to Test Methods and Specifications for Electrical Insulating Oils of Petroleum Origin 4 D 396 Specification for Fuel Oils5 D 1659 Test Method for Maximum Fluidity Temperature of Residual Fuel Oil6 D 2500 Test Method for Cloud Point of Petroleum Oils5 D 3245 Test Method for Pumpability of Industrial Fuel Oils7 E 1 Specification for ASTM Thermometers 8 E 77 Test Method for Inspection and Verification of Thermometers 8 2.2 IP Standards: Specifications for IP Standard Thermometers 9
This test method is under the jurisdiction of ASTM Committee D-2 on Petroleum Products and Lubricants and is the direct responsibility of Subcommittee D02.07 on Flow Properties. Current edition approved Nov. 10, 1996. Published January 1997. Originally published as D 97 - 27. In 1927, revised and repl_~ed__former D 47. Last previous edition D 97 - 96. In the IP, this test method is under the jurisdiction of the Standardization Committee. 2 The cloud point procedure formerly part of thistestmethod now ~ as Test Method D 2500. 3 Statements defining this test and its .significance when appfied to electrical insulating oils of mineral origin will be found in Guide D 117. 4 Annual Book of A S T M Standards, Vol 10.03. s Annual Book of A S T M Standards, Vol 05.01. 6 Discontinued; see 1984 Annual Book of A S T M Standards, Voi 05.01. 7 Annual Book of ASTM Standards, Vol 05.02 a Annual Book of A S T M Standards, Vol 14.03. 9 Methods for Analysis and Testing, IP Standards for Petroleum and its Products, Part 1, Vol 2.

3. Terminology 3.1 Definitions: 3.1.1 black oil, n--lubricant containing asphaltic materials. Black oils are used in heavy-duty equipment applications, such as mining and quarrying, where extra adhesiveness is desircxi. 3.1.2 cylinder stock, n--lubricant for independently lubricated engine cylinders, such as those of steam engines and air compressors. Cylinder stock are also used for lubrication of valves and other elements in the cylinder area. 3.1.3 residual fuel, n--a liquid fuel containing bottoms remaining from crude distillation or thermal cracking; sometimes referred to as heavy fuel oil. 3.1.3.1 Discussion--Residual fuels comprise Grades 4, 5, and 6 fuel oils, as defined in Speofication D 396. 4. Summary of Test Method 4.1 After preliminary heating, the sample is cooled at a specified rate and examined at intervals of 3C for flow characteristics. The lowest temperature at which movement of the specimen is observed is recorded as the pour point. 5. Significance and Use 5.1 The pour point of a petroleum specimen is an index of the lowest temperature of its utility for certain applications. 6. Apparatus 6.1 Test Jar, cylindrical, of clear glass, fiat bottom, 33.2 to 34.8-mm outside diameter, and 115 to 125 mm in height. The inside diameter of the jar can range from 30.0 to 32.4 ram, within the constraint that the wall thickness be no greater than 1.6 ram. The jar shall have a line to indicate a sample height 54 _+ 3 mm above the inside bottom. 6.2 Thermometers, having the following ranges and conforming to the requirements prescribed in Specification E l for thermometers:
Thermometer High cloud and pour Low cloud and pour Melting point Temperature Range -38 to + 50"C -80 to +20"C +32 to + 127"C Theilnometer Number ASTM IP 5C 6C 6 IC IC 2C 63C

6.2.1 Since separation of liquid column thermometers occasionally occurs and may escape detection, thermometers should be checked immediately prior to the test and used 87

~) D 97
only if they prove accurate within _IC (for example ice point). 6.3 Cork, to fit the test jar, bored centrally for the test thermometer. 6.4 Jacket, watertight, cylindrical, metal, flat-bottomed, 115 + 3-mm depth, with inside diameter of 44.2 to 45.8 mm. It shall be supported in a vertical position in the cooling bath (see 5.7) so that not more than 25 mm projects out of the cooling medium, and shall be capable of being cleaned. 6.5 Disk, cork or felt, 6 mm thick to fit loosely inside the jacket. 6.6 Gasket, to fit snugly around the outside of the test jar and loosely inside the jacket. The gasket may be made of rubber, leather, or other material that is elastic enough to cling to the test jar and hard enough to hold its shape. Its purpose is to prevent the test jar from touching the jacket. 6.7 Bath or Baths, maintained at prescribed temperatures with a firm support to hold the jacket vertical. The required bath temperatures may be obtained by refrigeration if available, otherwise by suitable freezing mixtures. Freezing mixtures commonly used for temperatures down to those shown are as follows:
For Temperatures Down
Ice and water

NOTE 7 - - I t is known that some materials, when heated to a temperature higher than 45"C during the preceding 24 h, do not yield the same pour point results as when they are kept at room temperature for 24 h prior to testing. Examples of materials which are known to show sensitivity to thermal history are residual fuels, black oils, and cylinder stocks.

Crushed ice and sodium chloride Crushed ice and calcium chloride crystals Acetone or petroleum naphtha (see Section 6) chilled in a covered metal beaker with an ice-salt mixture to -12C then with enough solid carbon dioxide to give the desired temperature.

9"C -12"C -27"(2 -57"(2

NOTE l - - T h e r e are automatic pour point testers available and in use which may be advantageous in the saving of test time, permit the use of smaller samples, and have other factors which may merit their use. If automatic testers are used, the user must ensure that all of the manufacturer's instructions for calibration, adjustment, and operation of the instrument are followed. It must be reported that the pour point was determined by an automatic instrument. Precision of automatic pour point testers has not been determined. In any case of dispute, the pour point as determined by the manual method described herein shall be considered the reference test.

7. Reagents and Materials 7.1 The following solvents of technical grade are appropriate for low-temperature bath media. 7.1.1 Acetone
NOTE 2: Warning--Extremely flammable.

7.1.2 Alcohol, Ethanol


NOTE 3: WarningmFlammable.

7.1.3 Alcohol, Methanol


NOTE 4: Warnlng--Flammable. Vapor harmful.

7.1.4 Petroleum Naphtha NOTE 5: Warning---Combustible. Vapor harmful. 7.1.5 Solid Carbon Dioxide
NOTE 6: Warning--Extremely cold -78.5C.

8. Procedure 8.1 Pour the specimen into the test jar to the level mark. When necessary, heat the specimen in a water bath until it is just sufficiently fluid to pour into the test jar.

8. l. l Samples of residual fuels, black oils, and cylinder stocks which have been heated to a temperature higher than 45"C during the preceding 24 h, or when the thermal history of these sample types is not known, shall be kept at room temperature for 24 h before testing. Samples which are known by the operator not to be sensitive to thermal history need not be kept at room temperature for 24 h before testing. 8.1.2 Experimental evidence supporting elimination of the 24-h waiting period for some sample types is contained in a research report, t0 8.2 Close the test jar with the cork carrying the high-pour thermometer (5.2). In the case of pour points above 36"C, use a higher range thermometer such as IP 3C or ASTM 61C. Adjust the position of the cork and thermometer so the cork fits tightly, the thermometer and the jar are coaxial, and the thermometer bulb is immersed so the beginning of the capillary is 3 mm below the surface of the specimen. 8.3 For the measurement of pour point, subject the specimen in the test jar to the following preliminary treatment: 8.3.1 Specimens Having Pour Points Above -33"C--Heat the specimen without stirring to 9"C above the expected pour point, but to at least 45"C, in a bath maintained at 12C above the expected pour point, but at least 48C. Transfer the test jar to a water bath maintained at 24C and commence observations for pour point. 8.3.2 Specimens Having Pour Points of-33=C and Below-Heat the specimen without stirring to 45C in a bath maintained at 48"(2 and cool to 150C in a water bath maintained at 6*C. Remove the high cloud and pour thermometer, and place the low cloud and pour thermometer in position. 8.4 See that the disk, gasket, and the inside of the jacket are clean and dry. Place the disk in the bottom of the jacket. Place the gasket around the test jar, 25 mm from the bottom. Insert the test jar in the jacket. Never place a jar directly into the cooling medium. 8.5 After the specimen has cooled to allow the formation of paraffin wax crystals, take great care not to disturb the mass of specimen nor permit the thermometer to shift in the specimen; any disturbance of the spongy network of wax crystals will lead to low and erroneous results. 8.6 Pour points are expressed in integers that are positive or negative multiples of 30C. Begin to examine the appearance of the specimen when the temperature of the specimen is 9"C above the expected pour point (estimated as a multiple of 3=C). At each test thermometer reading that is a multiple of 30C below the starting temperature remove the test jar from the jacket. To remove condensed moisture that limits visibility wipe the surface with a clean cloth moistened in alcohol (ethanol or methanol). Tilt the jar just enough to ascertain whether there is a movement of the specimen in the test jar. The complete operation of removal, wiping, and
m Available from ASTM Headquarters. Request RR:D02-1377. o

88

10 D 97
replacement shall require not more than 3 s. 8.6.1 If the specimen has not ceased to flow when its temperature has reached 27"C, transfer the test jar to the next lower temperature bath in accordance with the following schedule: Specimen Specimen Specimen Specimen Specimen is at is at is at is at is at +27C, move to 0C bath, +9C, move to -18"C bath, -6C, move to -33"C bath, -24"C, move to -51"C bath, -42"C, move to -69C bath. in 7.1 through 7.7 is the upper (maximum) pour point. If required, determine the lower (minimum) pour point by heating the sample while stirring to 105*C, pouring it into the jar, and determining the pour point as described in 7.4 through 7.7.

8.6.2 As soon as the specimen in the jar does not flow when tilted, hold the jar in a horizontal position for 5 s, as noted by an accurate timing device and observe carefully. If the specimen shows any movement, replace the test jar immediately in the jacket and repeat a test for flow at the next temperature, 3"C lower. 8.7 Continue in this manner until a point is reached at which the specimen shows no movement when the test jar is held in a horizontal position for 5 s. Record the observed reading of the test thermometer. NOTE 8--To determine compliance with existing specifications having pour point limits at temperatures not divisible by YC, it is acceptable practice to conduct the pour point measurement according to the following schedule: Begin to examine the appearance of the specimen when the temperature of the specimen is 9"C above the specification pour point. Continue observations at 3"C intervals as described in 7.6 and 7.7 until the specificationtemperature is reached. Report the sample as passing or failing the specification limit. 8.8 For black specimen, cylinder stock, and nondistillate fuel specimen, the result obtained by the procedure described
THERMOMETER

9. Calculation and Report 9.1 Add 3"C to the temperature recorded in 7.7 and report the result as the Pour Point, ASTM D 97. For black oil, and so forth, add 3"C to the temperature recorded in 7.7 and report the result as Upper Pour Point, ASTM D 97, or Lower Pour Point, ASTM D 97, as required. lO. Precision and Bias 10.I Lubricating Oil and Distillate and Residual Fuel Oil.2 10.1.1 Repeatability--The difference between successive test results, obtained by the same operator using the same apparatus under constant operating conditions on identical test material, would in the long run, in the normal and correct operation of this test method, exceed 3"C only in one case in twenty. Differences greater than this should be considered suspect. 10.1.2 Reproducibility--The difference between two single and independent test results, obtained by different operators working in different laboratories on identical test material, would in the long run, in the normal and correct operation of this test method, exceed 6"C only in one case in twenty. Differences greater than this should be considered suspect.

44.2 - 45.8 I9. 3e - 32.4 I D 332 - 3'~80D

CORK

JACKET
25 MAX.

I~ L
TEST JAR FILL LEVEL

COCLANT LEVEL

GASKET

COOLING

BATH

~o

DIS<
N O ~ E ~ X . ' m i O e S are in ~ (not to scale). FIG. 1

Apparatus for Pour Point Test

89

~) D 97
10.2 Bias--There being no criteria for measuring bias in these test-product combinations, no statement of bias can be made. 10.3 The precision statements were prepared with data on ten new (unused) mineral oil-based lubricants and sixteen assorted fuel oils tested by twelve cooperators. The mineral oil-based lubricants had pour points ranging from - 4 8 to -6"C while the fuel oils had pour points ranging from - 3 3 to +51 C. The following precision data were obtained:
Mineral Oil Lubricants 95 % Confidence Repeatability, "C Reproducibility, *C 2.87 6.43 Fuel Oils 2.52 6.59

APPENDIX

(Nonmandatory Information)
Xl. TEST FOR FLUIDITY OF A RESIDUAL F U E L OIL AT A SPECIFIED T E M P E R A T U R E Xl.1 General X I.I.1 The low-temperature flow properties of a waxy fuel oil depend on handling and storage conditions. Thus, they may not be truly indicated by pour point. The pour point test does not indicate what happens when an oil has a considerable head of pressure behind it, such as when gravitating from a storage tank or being pumped along a pipeline. Failure to flow at the pour point is normally attributed to the separation of wax from the fuel; however, it can also be due to the effect of viscosity in the case of very viscous fuel oils. In addition pour points of residual fuels are influenced by the previous thermal history of the specimens. A loosely knit wax structure built up on cooling of the oil can be normally broken by the application of relatively little pressure. X1.1.2 The usefulness of the pour point test in relation to residual fuel oils is open to question, and the tendency to regard the pour point as the limiting temperature at which a fuel will flow can be misleading. The problem of accurately specifying the handling behavior of fuel oil is important, and because of the technical limitations of the pour point test, various pumpability tests have been devised to assess the low-temperature flow characteristics of heavy residual fuel oils. Test Method D 3245 is one such method. However, most alternative methods tend to be time-consuming and as such do not find ready acceptance as routine control tests for determining low-temperature flow properties. One method which is relatively quick and easy to perform and has found limited acceptance as a "go-no-go" method is based on the appendix method to the former Test Method D 1659 - 65. The method is described as follows. Xl.2 Scope X I.2.1 This method covers the determination of the cooled at the specified temperature for 30 rain in the standard U-tube and is tested for movement under prescribed pressure conditions.

Xl.5 Significance and Use


X1.5.1 This method may be used as a "go-no-go" procedure for operational situations where it is necessary to ascertain the fluidity of a residual oil under prescribed conditions in an as-received condition. The conditions of this method simulate those of a pumping situation where the oil is expected to flow through a 12-mm pipe under slight pressure at a specified temperature. Fluidity, like Test Method D 97, is used to define cold flow properties. It differs from D 97, however, in that (a) it is restricted to residual fuel oil and (b) a prescribed pressure is applied to the sample. The latter represents an attempt to overcome the technical limitations of the Pour Point Method where gravity-induced flow is the criterion. Test Method D 3245, represents another method for predicting field performance in cold flow conditions. Test Method D 3245, however, does have limitations and may not be suitable for use with very waxy fuel oils which solidify so rapidly in the chilling bath that a reading cannot be obtained under the conditions of the test. It is also a time-consuming test and therefore not suitable for routine control testing.

Xl.6 Apparatus Xl.6.1 Glass U-Tubes, 150 m m high, having a uniform


internal diameter of 12.5 + 1 m m and a radius of curvature, measured to the outside curve of the tube of 35 m m (Fig. Xl.l). XI.6.2 Thermometers--Thermometers having a range from - 3 8 to +50"C and conforming to the requirements of Thermometer 5C as prescribed in Specification E 1, shall be used for insertion in the glass U-tubes and for measuring the temperatures of the baths. XI.6.3 Fluidity Temperature Test Bath ~ consists of a reservoir, a stirrer, and a motor and pump to circulate coolant through the coils of the tubing placed in the bottom of the test bath and passing through the cold bath. The flow of coolant through these coils can be controlled by a thermostat and a solenoid valve. It is possible that, where
t I A kinematic viscosity bath is usually satisfactory.

fluidity of a residual fuel oil at a specified temperature in an


as-received condition.

Xl.3 Definition X1.3.1 fluidity temperature--the sample when tested in


an as-received condition is considered "fluid at the temperature of the test" if it will flow 2 m m in 1 min in a 12.5 m m U-tube under a maximum pressure of 152 m m of mercury.

Xl.4 Summary of Test Method


X 1.4.1 A sample of fuel in its as-received condition is 90

ll~ D 97
ASTM 5C Thermometer

To Vacuum Controller

Bung

2J/l ,

Bath Medium

150

75
m

Sample~ _
NOTE--NI dimensionsare In mlmeVes FIG. X1.1 I)iq~ of U-tube in Flukll~/Tea~pemture Test Bath

justified by the quantity of work, more than one such bath could be utilized to permit concurrent testing at more than one temperature (Fig. X1.2). X1.6.4 Mercury Manometer calibrated in lO-mm divisions with a distinguishing mark at 152 m m (equivalent to 20.3 Ida). X1.6.5 Automatic Vacuum Controller 12 as shown in Figs XI.3 and XI.4---a device that gradually increased the vacuum applied to one end of the U-tube at the specified rate of I0 mm/4S.
t2 T I ~ appmatus may be shop fabricated. Details of special parts ate indicated in Figs. XI.3 and XI.4. Alternatively the appmatus can be purchased.

Xl.7 Preparation of Apparatus


XI.7.1 Adjust the automatic vacuum controller as follows: close the stopcock on the tube connecting the automatic vacuum controller to the fluidity tester. A pinchcock on the rubber tube will serve as well as a stopcock. Wind the thread attached to the steel rod around the pulley on the synchronous motor until the end of the rod is about 15 m m above the zero level of the mercury in the control manometer. Turn on the power switch. The thread will begin to unwind, lowering the steel rod. When the rod contacts the mercury, the relay will open the solenoid valve in the vacuum line and air will be pumped from the system at a rate limited by the needle valve. Adjust this needle valve

91

o 97
until the descending mercury in the control manometer just leads the rod, reducing the relay operation to a minimum. When properly adjusted, the pulsations caused by the opening and closing of the solenoid valve should not exceed +__ ram. In this manner the pressure in the system will be 1 reduced gradually at a rate governed by the descent of the steel rod. Xl.8 Procedure X1.8.1 Pour the sample as received into a thoroughly cleaned and dry standard fluidity U-tube, without contacting the upper walls of the tube, until the vertical height of the sample in the U-tube is 38 mm. Insert in one leg of each U-tube an ASTM Thermometer 5C in a cork that has been grooved to permit the passage of air. The thermometer must be placed in the center of the tube and its bulb immersed so that the beginning of the capillary is 3 m m below the surface of the specimen. X1.8.2 Fix the tube in the bath set at the specific temperature, immersed to a depth of approximately 75 ram. Control the bath and sample temperatures within __.I*C and _0.5"C, respectively, of the specified temperature of the test. XI.8.3 Maintain the sample at the specified temperature for 30 min __+ 30 s, with the U-tube connected to the

FIG. X1.2

Fluidity Temperature Apparatus

92

dl~ D 97
C 0

Wiring Flexible Wirey ~

Diogrom

O_

E E b

O3 ~r
_.m

5~

355-mm

:
0-ram
Front View

m Wire Iocl

Bock View
1 1 ~ cord to outlet

+--26mm d~un.facepuny.
2--Thread 3--Steel rod.

12~Syr~'-.-cq-~.~smoto.
13--Plywood of approximately 10rnm thickness 14= M.'tliT~terscale.

4---Swltch-DPST. 5~Tee 90ram long. 6--Needle valve.


7--Rubber or plastic tublng. 8--6mm heat ~ glass tube. 9.--Solene~ valve. lO--Electric relay. FiG. X l . 3

15~4 liter boffie


16--0.5 mm heat resistant gdassCal01ary. 17--To vaoJum line.

18---Rod hogder.

AssemMy Automatic Vacuum Controller Apparatus

automatic vacuum controller, and the stopcock or pinchclamp open. Wind the thread on the pulley attached to the synchronous motor. Turn the power switch to the ON position. Apply suction automatically to the U-tube at the prescribed rate. Observe any movement of the specimen during a one-minute interval which is the time required to apply 152-mm Hg vacuum to the specimen in the U-tube. Immediately disconnect the U-tube from the automatic vacuum controller, turn off the power switch and rewind the 93

thread. If the specimen has moved 2 mm or more during the time (1 min) the suction was applied, the specimen is considered fluid at the temperature of the test. X1.9 Report X1.9.1 Report the fluidity of the sample at a specified temperature as follows: X 1.9.1.1 If the sample fulfdls the conditions of flow, as