ASTM D02 Committee Petroleum Testing Aids

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Address 100 Barr Harbor Drive Phone 610.832.9500

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COMMITTEE D02 ON PETROLEUM PRODUCTS, LIQUID FUELS, AND LUBRICANTS
CHAIRMAN: RANDY F JENNINGS, TENNESSEE DEPT OF AGRIC, P O BOX 40627, NASHVILLE, TN 37204, UNITED STATES
(615) 837-5327, FAX: (615) 837-5335, E-MAIL: RANDY.JENNINGS@TN.GOV
FIRST VICE CHAIRMAN: JAMES J SIMNICK, BP AMERICA, 150 W W ARRENVILLE RD, NAPERVILLE, IL 60563, UNITED STATES (630)
420-5936, FAX: (630) 420-4831, E-MAIL: SIMNICJJ@BP.COM
SECOND VICE CHAIRMAN: MICHAEL A COLLIER, PETROLEUM ANALYZER CO LP, 21114 HWY 113, CUSTER PARK, IL 60481, UNITED
STATES (815) 458-0216, FAX: (815) 458-0217, E-MAIL: MICHAEL.COLLIER@PACLP.COM
SECOND SECRETARY: HIND M ABI-AKAR, CATERPILLAR INC, BLDG H3000, OLD GALENA ROAD, MOSSVILLE, IL 61552, UNITED
STATES (309) 578-9553, E-MAIL: ABI-AKAR_HIND@CAT.COM
SECRETARY: SCOTT FENWICK, NATIONAL BIODIESEL BOARD, PO BOX 104848, JEFFERSON CITY, MO 65110-4898,
UNITED STATES (800) 841-5849, FAX: (537) 635-7913, E-MAIL: SFENWICK@BIODIESEL.ORG
STAFF MANAGER: ALYSON FICK, (610) 832-9710, E-MAIL: AFICK@ASTM.ORG
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ASTM D02
PROFICIENCY TESTING PROGRAM
AIDS–TO–THE ANALYST
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R. A. KISHORE NADKARNI
MILLENNIUM ANALYTICS, INC.
EAST BRUNSWICK, NJ
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AUGUST 2014
This document contains a selection of more widely used test methods (about 75) in the petroleum
and lubricant testing areas and that are used in ASTM’s Proficiency Testing Programs under the
jurisdiction of D02.CS 92 Committee. Many of these suggestions are incorporated into the text
of the relevant standards, but could be overlooked in reading through long passages in the
standards. Hence, they are summarized here for convenience. The test methods are grouped
alphanumerically in Table A, and as far as possible by subject matter and/or technique used in
Table B. These aids are NOT a substitute for original complete ASTM Standard Test Methods.
Before operation of any test, the original test method must be fully perused.
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Table A
Practical Hints for Test Method Operation
(Alphanumeric List)
ASTM Analysis Matrix Page
Standard
D56 Tag Closed Cup Flash Point Liquids 27
D92 COC Flash Point Petroleum Products 28
D93 PMCC Flash Point Petroleum Products 28
D94 Saponification Number Lubricating Oils 87
D97 Pour Point (Manual) Petroleum Products 85
D129 Sulfur by High Temperature Method Petroleum Products 89
D287 API Gravity Petroleum Products 20
D323 Reid Vapor Pressure Petroleum Products 91
D381 Gum Content by Jet Evaporation Fuels 31
D445 Kinematic Viscosity Petroleum Products 32
D482 Ash Petroleum Products 11
D664 Acid Number by Potentiometric Petroleum Products 6
Titration
D808 Chlorine Petroleum Products 17
D874 Sulfated Ash Lubricating Oils 11
D892 Foaming Characteristics Lubricating Oils 30
D974 Acid & Base Number Petroleum Products 7
D1298 Density Petroleum Products 20
D1318 Sodium by Flame Photometry Residual Fuel Oil 88
D1500 ASTM Color Petroleum Products 19
D2500 Cloud Point (Manual) Petroleum Products 17
D2622 Sulfur by WD-XRF Petroleum Products 59
D2896 Base Number Petroleum Products 13
D2983 Brookfield Low Temperature Lubricants 16
Viscosity
D3228 Nitrogen by Kjeldahl Method Petroleum Products 81
D3237 Lead by Atomic Absorption Gasoline 38
Spectrometry
D3339 Acid Number by Colorimetric Petroleum Products 7
Titration
D3605 Trace Metals by AAS Gas Turbine Fuels 39
D3828 Flash Point by Small Scale Closed Petroleum Products 29
Cup Tester
D3831 Manganese by AAS Gasoline 41
D4052 Density by Digital Density Meter Petroleum Products 20
D4294 Sulfur by ED-XRF Petroleum Products 65
D4377 Water by Karl Fischer Titration Crude Oils 94
D4530 Microcarbon Residue Petroleum Products 80
D4628 Metals by AAS Lubricating Oils 36
D4629 Nitrogen by Chemiluminescence Petroleum Products 81
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D4684 Yield Stress and Apparent Viscosity Petroleum Products 91

using Mini Rotary Viscometer
D4739 Base Number Petroleum Products 14
D4927 Metals by WD-XRF Additives and Lubricants 67
D4951 Metals by ICP-AES Additives and Lubricants 46
D5002 Density Crude Oils 21
D5056 Trace Metals by AAS Petroleum Coke 42
D5059 Lead by WD-XRF Gasoline 69
D5184 Al and Si by AAS or ICP-AES Fuel Oils 47
D5185 Metals by ICP-AES Fresh and Used Oils 49
D5291 C-H-N Instrumental Analysis Petroleum Products 85
D5293 Apparent Viscosity using Cold Petroleum Products 9
Cranking Simulator
D5453 Sulfur by UV-Fluorescence Petroleum Products 89
D5501 Ethanol & Methanol by GC Fuels 21
D5600 Trace Metals by ICP-AES Petroleum Coke 51
D5708 Metals by ICP-AES Crude Oils and Fuel Oils 53
D5762 Nitrogen by Chemiluminescence Petroleum Products 81
D5771 Cloud Point – Optical Detection Petroleum Products 18
Stepping Cooling Method
D5772 Cloud Point – Linear Cooling Rate Petroleum products 18
Method
D5773 Cloud Point- Constant Cooling Rate Petroleum Products 18
Method
D5800 Evaporation Loss by Noack Method Lubricating Oils; Base Oils 22
D5863 Metals by AAS Crude Oils and Fuel Oils 44
D5949 Pour Point Petroleum Products 86
D6304 Water by Coulometric Titration Petroleum Products 95
D6334 Sulfur by WD-XRF Petroleum Products 61
D6376 Trace Metals by WD-XRF Petroleum Coke 70
D6443 Metals by WD-XRF Additives and Lubricants 71
D6445 Sulfur by ED-XRF Gasoline 72
D6481 Metals by ED-XRF Lubricating Oils 75
D6667 Volatile Sulfur by UV-Fluorescence Gaseous Products 90
D7039 Sulfur by MWD-XRF Petroleum Products 62
D7040 Phosphorus by ICP-AES Lubricating Oils 55
D7042 Dynamic Viscosity and Density Petroleum Liquids 34
D7279 Houllion Kinematic Viscosity Petroleum Products 35
D7689 Cloud Point by Mini Method Petroleum Products 19
D7691 Elemental Analysis by ICP-AES Crude Oils 56
D7751 Additive Elements by ED-XRF Lubricating Oils 75
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Table B
Practical Hints for Test Method Operation
(Subject List)
Analysis Test Method Page

Acid Number- Potentiometric Titration D664 6
- Colorimetric Titration D974 7
- Semi-Micro Color Indicator Titration D3339 7
API Gravity D287 20
Apparent Viscosity using Cold Cranking Simulator D5293 9
Ash – Petroleum Products D482 11
Base Number - Perchloric Acid Potentiometric Titration D2896 13
- HCl Potentiometric Titration D4739 14
- Colorimetric Titration D974 7
Brookfield Viscosity at Low Temperatures D2983 16
Chlorine D808 17
Cloud Point - Manual D2500 17
- Optical Detection Stepping Cooling D5771 18
Method
- Linear Cooling Rate Method D5772 18
- Constant Cooling Rate Method D5773 18
- Mini Method D7689 19
Color – ASTM D1500 19
Density - Hydrometer D287 20
- Hydrometer D1298 20
- Digital Density Meter D4052 20
- Of Crude Oils by Digital Density Meter D5002 21
- By Stabinger Viscometer D7042 34
Ethanol and Methanol in Fuels D5501 21
Evaporation Loss by Noack Method D5800 22
Flash Point - Cleveland Open Cup D92 28
- Penskey Martens Closed Cup D93 28
- Seta Closed Cup D3828 29
- Tag Closed Cup D56 27
Foaming Tendency D892 30
Gum Content by Jet Evaporation D381 31
Kinematic Viscosity D445 32
- By Houillon Viscometer D7279 35
Lead - Atomic Absorption Spectrometry D3237 38
- WD-XRF D5059 69
Manganese in Gasoline by AAS D3831 41
Metals in Lubricating Oils by by Atomic Absorption D4628 36
Spectrometry
Metals in Gas Turbine Fuels by AAS and FES D3605 39
Metals in Petroleum Coke by AAS D5056 42
- by WD-XRF D6376 69
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Metals in Crude Oils by AAS D5863 44

Metals in Additives by ICP-AES D4951 46
Metals in Fuel Oils by ICP-AES and AAS D5184 47
Metals in Lubricating Oils by ICP-AES D5185 49
Metals in Petroleum Coke by ICP-AES D5600 51
Metals in Crude Oils by ICP-AES D5708 53
Metals in Crude Oils by ICP-AES D7691 56
Phosphorus in GF 4 Oils by ICP-AES D7040 55
Sulfur by ED-XRF D6445 71
Metals in Lubricating Oils by ED-XRF D6481 74
Metals in Lubricating Oils by ED-XRF D7751 74
Metals in Lubricants and Additives by WD-XRF D4927 67
by WD-XRF D6443 70
Microcarbon Residue of Petroleum Products D4530 80
Nitrogen - Kjeldahl Titration D3228 81
- Chemiluminescence (Syringe) D4629 81
- Instrumental D5291 85
- Chemiluminescence (Boat) D5762 81
Pour Point - Manual D97 85
- Automatic Pressure Pulsing Method D5949 86
- Automatic Tilt Method D5950 86
- Rotational Method D5985 86
- Robotic Tilt Method D6892 87
Reid Vapor Pressure D323 91
Saponification Number of Lubricating Oils D94 87
Sodium in Residual Fuel Oil D1318 88
Sulfated Ash – Additives D874 11
Sulfur by High Pressure Decomposition Device D129 89
Sulfur by Combustion and UV-Fluorescence Detection D5453 89
Sulfur by Combustion and On-Line Detection by UV- D6667 90
Fluorescence
Sulfur in Petroleum Products by ED-XRF D4294 65
Sulfur in Petroleum Products by WD-XRF D2622 59
Sulfur in Gasoline by WD-XRF D6334 61
Yield Stress and Apparent Viscosity using Mini Rotary D4684 91
Viscometer
Water in Crude Oil D4377 94
Water by Coulometric Titration Method D6304 95
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ACID NUMBERS BY TITRATIONS
Values obtained by different acid number methods may or may not be numerically the same;
hence, the test method required must not be switched arbitrarily from one to another.
Acid Number of Petroleum Products by

Potentiometric Titration: D664
1. Alcoholic HCl solution (0.1 or 0.2 M) must be standardized frequently enough to detect
normality changes of 0.0005 by potentiometric titration with 0.1 N alcoholic KOH solution.
1a. Store the standard alcoholic KOH solution in a chemically resistant bottle. It must be
protected from atmospheric carbon dioxide by means of a guard tube containing soda
lime or soda non-fibrous silicate absorbents, and such that it does not come in contact
with cork, rubber, or saponifiable stopcock grease.
2. Isopropyl alcohol used must be anhydrous. If necessary, dry it over Linde type 4A molecular
sieve or by distillation through a multiple plate column.
3. Standard alcoholic KOH solution must be protected from absorbing atmospheric carbon
dioxide by means of a guard tube containing soda lime or sodium silicate absorbents.
4. Standardize the alcoholic KOH solution frequently enough to detect normality changes of
0.0005 by potentiometric titration against standard potassium hydrogen phathalate.
5. Electrode response and cleanliness are critical parameters for this method. Failure to follow
the correct electrode preparation instructions is known to give wrong results.
6. Follow the instructions given in Section 8 of the Test Method D664 for the preparation,
testing, and maintenance of the electrodes. Electrode performance check is given in
Appendix X1 of Test Method D664. Electrodes must be tested before use since they have a
limited shelf life.
7. Be sure to use the correct electrolyte solution as per the test method and not as suggested by
an instrument vendor. Different electrolytes may yield different results.
8. Use only the amount of sample recommended in Table 1 for titration. Sample weights may
greatly affect the results for certain types of samples.
9. A blank value for the titration solvent should be determined each testing day by titration prior
to use.
10. When acid numbers are about or below 0.1 are expected, better precision can be obtained by
modifying the method; e.g., using a 0.01 or 0.05 M alcoholic KOH solution, or increasing the
sample size above 20 g, or by switching from a manual operated burette to an automated one
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that can dispense smaller increments of the KOH solution. However, the precision estimates
given in the standard may not be applicable in such cases.
11. As used oil can change appreciably in storage, test the samples as soon as possible after
removal from the lubricating system and note the dates of sampling and testing.
12. Strict observance of the sampling procedure is necessary since the sediment in the sample
itself is acidic or basic. Failure to obtain a representative sample causes serious errors. This
can be achieved by heating and vigorously shaking until all sediment is homogenously
dispersed.
13. Test Method B should be used only for the analysis of biodiesel and biodiesel blends. All
other petroleum products and lubricants should be analyzed with Test Method A.
Acid and Base Number by Color Indicator Titration: D974
1. Same notes as # 1, 2, 3, 4, 8, and 9 above for Test Method D664.
2. To observe the end point of a dark colored oil, shake the flask vigorously to produce
momentarily a slight foam when the color change occurs as the last few drops of titrant are
added, and observe the titration under a white fluorescent lamp at bench top level.
3. Not all brands of p-naphtholbenzein are suitable for use in this titration. See the criteria given
in the test method appendix.
Acid Number of Petroleum Products by Semi-Micro

Color Indicator Titration: D3339
1. See the notes above for Test Methods D664 and D974. They also apply to this Test Method.
2. Dark colored oils may be more difficult to analyze by this method than by the potentiometric
titration method D664. The acid numbers obtained by these two methods may or may not be
numerically the same but should be of the same order of magnitude.
3. All entrances and exits to the buret and reservoir from the titrant reservoir must be connected
to the absorption tubes to remove atmospheric carbon dioxide and water. Precautions must be
taken to prevent introduction of any soda-lime from the absorption tubes into the titrant
reservoir or the buret.
4. The top of the titration solvent must be stoppered and connected to an absorption tube to
remove atmospheric carbon dioxide and water.
5. P-Naphtholbenzein indicator solution must meet the requirements given in the appendix of
the standard. Not all brands qualify for use in this test method.
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6. In order to obtain precise results and a stable end point color change, it is especially
important that the nitrogen purge gas be free of carbon dioxide.
7. Store the KOH titrant in a chemically resistant dispensing bottle out of contact with cork,
rubber, or saponifiable stopcock lubricant, and protected by a guard tube containing soda-
lime. Minimize exposure of the titrant to light by storing in dark or in an amber bottle or by
wrapping the bottle with aluminum foil.
8. Ensure that the final normality of the KOH titrant is 0.01 ± 0.002 molar.
9. Because of the relatively large coefficient of cubic expansion of organic liquids, such as
propanol-2-ol, the standard alcoholic solutions should be standardized at a temperature close
to that employed in the titration of the samples.
10. Standardize the KOH titrant frequently enough to detect changes of 0.0003 M.
11. Strict observance of the sampling procedure is necessary, since the sediment itself is acidic or
basic. Failure to obtain a representative sample will cause serious errors in analysis. Heat the
sample and thoroughly shake it until sediment is homogenously dispersed in the solution.
12. Limit the size of the sample taken for analysis to that specified in Table 1 of the standard.
Significant deviations from suggested weights will produce erroneous results.
13. Take a blank titration each day that samples are analyzed. Conduct this titration using the
procedure described in the method except omitting using the sample.
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APPARENT VISCOSITY USING COLD CRANKING

SIMULATOR: D5293
There are three CCS procedures under this standard: Manual, automated, and automatic
automated. Cannon is the sole supplier of all CCS instruments.
1. Ensure that there is good thermal contact between the temperature sensor and the thermal
wall in the stator. Clean the thermal well periodically and replace the small drop of high-
silver-containing heat transfer medium. Not doing this will affect the precision of calibration,
give inconsistent results, and require more frequent re-calibrations. Adjust the temperature of
the coolant to the viscometric cell to be at least 10 to 15°C below the test temperature.
2. If a thermometric cooling system is used in the instrument, the liquid cooling temperature of
the water or other appropriate liquid used in the refrigeration system (chiller) should be set to
approximately 5°C in order to maintain the sample test temperature.
3. The test method implies a temperature tolerance of ±0.5°C. The vendor (Cannon) suggests
that this should be closer to ±0.02°C. When the instrument is operating, the temperature set
point should be achieved within remaining 30 sec of running. If not, check the methanol bath,
the temperature probe, or the control board.
4. At each test temperature, calibrate with the oils listed in Table 1 of the standard for that
temperature. It is important to use the calibration standards that cover the entire viscosity
range. Instruments will slowly drift after calibration; hence, periodic checks are necessary. A
frequency of every three months is suggested.
5. If the sample in its container is received below the dew point temperature of the room, allow
the sample to warm to room temperature before opening the container. When the sample
contains suspended material, use a filter or a centrifuge to remove particles greater than 5 um
in size. Do not shake the sample of test oil; this leads to entrainment of air, and a false
viscosity reading.
6. Rotor and stator gap needs to be adjusted during calibration. Clearance may vary due to
changes in the sealing of O rings, shaft collars, and shaft changes. This may not be apparent
for Newtonian oils (i.e., standards used) but may affect the real samples. It is recommended
to change rotor/stator every two years. A gauge for adjusting rotor height would be helpful
during set-up. The rotor must not move up or down. If it does, collars must be adjusted. They
must be adjusted. They must be installed correctly. There is a right way and a wrong way.
Follow the instruction manual.
7. When only a narrow viscosity range of test liquids is to be measured, use a minimum of three
calibration oils (for automated CCS machines use a minimum of four) spanning the narrow
viscosity range of the oils to be tested.
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8. When check runs of calibration oils do not fall within ±5 % of the values calculated from the
calibration curve, recheck the calibration of the temperature sensor or rerun the calibration
oils.
9. If all oils listed in Table 1are not available, generally use the five highest viscosity level oils.
Since the calibration determination is a log-log function, analysis outside the standards range
may give a 10 to 30 % error.
10. For automated CCS machines, on start-up of a new instrument or when any part of the
viscometric cell or drive component (motor, belt, and so forth) is replaced, determine the
required motor current. Initially, recheck the motor current monthly until the change in the
motor current in consecutive months is less than 0.020 A, and every three months thereafter.
11. Ensure that the cooling bath is stirred during the operation of the instrument. Failure to do so
will permit large gradients in the temperature to exist in the cooling bath. These large
gradients will affect the sample temperature and reduce the precision of viscosity
measurements.
12. The use of blind reference samples is recommended for an overall check on all performances,
at six month intervals. These samples are available from the calibration oil supplier.
13. In operation of automated CCS instruments, care should be taken to ensure that the injection
tube does not reach to the bottom of the sample container placed in the machine, in order to
avoid drawing any sediment from the oil into the instrument.
14. Automatic units do not need solvent rinse; but may have residual effect from previously
analyzed high viscosity sample. It is a good practice to run a rinse sample of viscosity similar
to the next sample to be analyzed.
15. When the check runs of the calibration test samples or secondary standards do not fall within
±5 % of the expected values, the results are considered suspect.
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ASH FROM PETROLEUM PRODUCTS: D482

1. Certain ash forming metals may not be quantitatively retained in the ash. Use sulfated ash
procedure D874 in such cases.
2. This method should not be used for lubricating oils containing ash forming additives
including phosphorus and lead. This method should also not be used for used engine
crankcase oils.
3. Vigorous shaking of the sample may be necessary to ensure that the portion taken for ashing
is truly representative of the larger portion. Mix thoroughly for about 10 minutes by manual
or mechanical shaking to obtain a homogenous specimen.
4. Sample weight is critical. Be sure to use a large enough sample to enable obtaining
accurately weighable amount of ash residue.
5. Control the sample combustion so that no portion of the sample is ejected due to too vigorous
combustion.
5a. Do not leave the burning samples unattended by the operator.
6. Check the ashing furnace periodically to ensure a temperature of 775 ± 25°C by measuring
with a calibrated temperature measuring device.
7. Completely cool the crucible to room temperature in a desiccator NOT containing the
desiccant before weighing the ash residue.
7a. All crucibles should be weighed as soon as they have cooled.
SULFATED ASH FROM LUBRICATING

OILS AND ADDITIVES: D874
1. This test method should not be used for the analysis of used engine oils, oils containing lead,
or non-additive lubricating oils.
2. The presence of a number of metals, particularly B, Mg, Mo, P, and Zn causes low results
compared to the theoretical values. The difference between the two sets of results will
depend on the ashing temperature, time ashed, and composition of the metallic constituents
present in the oils. Sulfated ash results are generally 83% of the theoretical results.
2a. Samples containing magnesium do not react the same way as other alkali metals in this
test. If magnesium additives are present, interpret the data with caution.
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2b. Samples containing molybdenum can give low results because molybdenum compounds
are not fully recovered at the temperature of ashing.
2c. Since zinc sulfate slowly decomposes to its oxide in the ignition temperature specified in
the test method, samples containing zinc can give variable results unless the zinc sulfate
is completely converted to zinc oxide.
3. If the sulfated ash results obtained differ from the expected amount by more than a factor of
two, repeat the analysis with a different weight of sample.
4. For best results, use platinum dishes rather than Vycor, quartz, or porcelain dishes to prevent
contamination due to reaction between the burning sample, sulfuric acid, and the crucible
material. However, when phosphorus is present in the sample, do not use the platinum dishes.
5. Check the ashing furnace periodically to assure a temperature of 775 ± 25°C.
6. Be sure to use a large enough sample to enable obtaining accurately weighable amount of
sulfated ash residue. However, do not use more than 80 g of sample.
7. Be sure to carry out a blank through the entire procedure using sulfuric acid. Subtract the
blank from the results for samples containing 0.02 mass % or less of sulfated ash. When
using a low ash mineral oil to dilute the sample (see Section 9.3), run a mineral oil blank and
subtract the result.
8. Control the sample combustion so that no portion of the sample is ejected due to too vigorous
combustion.
9. Perform the ashing in stages described in Section 9. Failure to adhere to heating the dish or
crucible at 775 ± 25°C for the required 30 minutes could impact results. The experimental
data revealed that heating samples for extended periods of time (e.g., overnight) versus the
current method’s reheating time of 30 minute cycles can cause the sulfated ash values to
decrease with time. This finding was also confirmed by thermogravimetric analysis that
showed that the sample continues to lose weight as a function of time.
10. Completely cool the crucible to room temperature in a desiccator NOT containing a desiccant
before weighing the residue.
BASE NUMBERS OF PETROLEUM PRODUCTS BY

TITRATION
Values obtained by different base number methods (D974, D2896, and D4739) numerically may
or may not be the same; hence, the test method required must not be switched arbitrarily from
one to another. Test Method D2896 remains the preferable base number method of analysis due
to its superior precision, definitive end pointy, and historic large data base. Test Method D4739
is to be used exclusively for tracking base numbers for in-service oils.
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D2896: Perchloric Acid Titration

1. Some titration apparatus may be sensitive to interference by static electricity as evident from
erratic movements of the recorder pen or meter indicator when the titration assembly is
approached by the operator. In such cases the titration apparatus must be grounded. One way
of doing this is to surround the beaker closely with a cylinder of copper foil that is
electrically grounded.
2. Standardize or validate the perchloric acid solution, even if purchased as a known standard.
3. Perchloric acid and sodium acetate solutions must be standardized when first prepared and
periodically thereafter.
4. Because of the relatively large coefficient of volumetric expansion of organic liquids, the
acetous perchloric acid solution should be used within ±5°C of the temperature at which it
was standardized.
5. Electrode response and cleanliness are critical parameters in this test method. Failure to
follow the correct electrode preparation instructions is known to give wrong results. Follow
the instructions given in the standard for preparation, testing, and maintenance of the
electrodes.
6. Electrodes must be cleaned after each titration. See sections 10.3, 10.4 and Appendix X4 of
Test Method D2896. Do not allow the electrodes to remain immersed in titration solvent for
any appreciable period of time between titrations. Store the electrodes in distilled water when
not in use. Rinse the electrodes thoroughly with distilled water between analyses.
7. A blank value for the titration solvent must be determined every time prior to use.
8. Additives in the lubricating oils often cling to the electrodes and leave behind a residue that
decreases sensitivity. This results in an erratic response rather than a smooth titration curve.
Visually check both electrodes frequently. If dirty, use a soft cloth dampened with
chlorobenzene or an equivalent solvent to clean both electrodes of the residue. If necessary,
thoroughly clean the electrodes as described above.
9. Some samples may produce multiple inflection points; preferably use the strongest inflection
point.
10. Strict observance of the sampling procedure is necessary since the sediment itself is acidic or
basic. Failure to obtain a representative sample negates a meaningful value obtained. This
can be achieved by heating the sample and vigorously shaking the sample containers
thoroughly before removing any specimen from them. If any sediment is present in the
sample container, heat the container as well as shake it before removing a specimen for the
test.
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11. Use the sample size based on the estimated base number given in the standard. Repeat the
analysis if the first result was outside the range listed.
13. It is especially important for Procedure B that great care is exercised in obtaining accurate
weight particularly for high base number samples which require small sample weights.
14. Because the base number can vary while the quality control sample is in storage, when an
out-of-control situation arises, the stability of the QC sample can be a source of error.
15. If an alternative solvent (e.g., mixed xylenes) is used instead of chlorobenzene, the two
solvents may provide statistically equivalent results, but the precision of the alternative
solvent results is worse than that obtained with chlorobenzene.
D4739: Hydrochloric Acid Titration
1. All comments above for D2896 also apply to D4739.
2. The precision of addition of the 0.100 mL increments of titrant must be ±0.001 mL for
automatic titrators and ±0.005 mL for manual buret.
3. Alcoholic KOH must be standardized frequently enough to detect normality changes of

0.0005 M by potentiometric titration with potassium hydrogen phthalate.
4. HCl titration with basic component is very slow; hence, the titration conditions specified
must be strictly adhered to.
5. Isopropyl alcohol must be anhydrous (<0.1 % water content). It can be dried by either
distillation through multiple plate column or over molecular sieve such as Linde Type 4A.
6. Irrespective of whether manual or automatic titrations are used, the procedure of fixed
increment, fixed time addition of titrant must be followed. Add 0.1 M HCl in 0.100 mL
increments throughout the titration with a 90 sec pause between each incremental addition.
7. Buffer stock solutions A and B must be used within two weeks of preparation.
8. Non-aqueous acid and base buffers must be used within one hour of their preparation.
9. When not in use, immerse the lower halves of the electrodes in either water (glass) or in LiCl
in isopropyl alcohol electrolyte (reference). Do not allow them to remain immersed in the
titration solvent for any appreciable period of time between titrations. While the electrodes
are extremely fragile, treat them carefully at all times.
15
10. Electrodes must be cleaned after each titration. See Section 8 and Appendix X2 of Test
Method D4739. Cleaning the electrodes thoroughly, keeping the ground-glass joint free of
foreign materials, and regular testing of the electrodes are important in obtaining repeatable
potentials.
11. Before and after using, blot-dry the glass electrode thoroughly with a clean cloth or a self-
absorbent tissue, and rinse with water. Wipe the reference electrode with a cloth or tissue.
Refer to the test method for further instructions.
12. Test the meter-electrode combination when first put into use or when new electrodes are
installed, and retest at intervals thereafter.
13. Daily determine for each electrode pair, the meter readings obtained with the freshly
prepared non-aqueous acidic buffer solution to be used for the determination of base
numbers.
14. The response of different glass electrodes to hydrogen ion activity is not the same. Hence, it
is necessary to establish regularly for each electrode system the meter reading corresponding
to the acidic and basic buffer solutions arbitrarily selected to represent the end point
15. Strict observance of the sampling procedure is necessary since the sediment itself is acidic or
basic. Failure to obtain a representative sample negates a meaningful value obtained. This
can be achieved by heating the sample and vigorously shaking the sample containers
thoroughly before removing any specimen from them. If any sediment is present in the
sample container, heat the container as well as shake it before removing a specimen for the
test.
16. Do not take more than 5 g or less than 0.1 g of the sample for analysis.
18. For each set of samples, make a blank titration of the same volume of titration solvent used
for the sample.
BROOKFIELD VISCOSITY OF LUBRICANTS: D2983

1. The test method specifies an air cooled cabinet controlled within ±0.3°C. If a liquid bath is
substituted, it must be able to replicate this cooling rate.
2. Thermometer or other temperature indicator device must be calibrated against a master

thermometer. Two thermometers should be used as a check against each other.
3. All spindles should be calibrated periodically. Periodically (depending on use but at least
every 3 months) inspect spindles for run-out (wobble) when attached to the Brookfield
viscometer.
16
4. It is a good laboratory practice to store spindles in a protective manner. Do not leave

composite spindles for extended periods in cleaning solvent.
5. Great care must be taken to assure proper spindle immersion with all reference oil runs.
Improper immersion may be reflected as an apparent temperature variation.
6. Do not adjust the bath temperature late in the sample conditioning period because the sample
viscosity may be significantly changed.
7. Maintenance of proper immersion depth is essential to getting good precision. An immersion

variation of as little as 1.2 mm from the dimple can produce a viscosity error.
8. Preheating step is important in this test and is designed to remove any memory effects that
may develop from previous low-temperature exposures or structure formations.
9. Automatic transmission fluids may be soaked for 6 hours; all other samples must be soaked
for 16 hours.
10. Do not open the cold box frequently during a long series of runs, since it can cause a
temperature rise in the oil. To minimize this effect, turn the air circulation device off when
the top is open, and do not leave it open unnecessarily. Allow some time for the temperature
in the cabinet to come to equilibrium after closure and before withdrawing another sample.
11. To avoid disturbing temperature control, it is best not to insert any of samples
simultaneously while Brookfield analyses are being conducted.
Chlorine in New and Used Petroleum Products: D808
1. Do not used decomposition pressure vessels with scratched inner surfaces.
2. A white oil blank must be run throughout the procedure.
3. Because of the tendency of chlorine to contaminate the walls of the pressure decomposition
vessel, do not analyze high and low chlorine samples alternatively. If a low chlorine sample
is analyzed after a high chlorine sample, repeat the low chlorine analysis. These duplicate
results should match within the repeatability of the method.
4. Thoroughly Wash the inside of the pressure decomposition vessel and terminals, etc. with
distilled water to collect all traces of chlorine.
5. Protect the silver chloride precipitate from light.

17
CLOUD POINT OF PETROLEUM PRODUCTS

There are several cloud point test methods including a manual and others based on physical
properties when the samples are cooled to cloud point temperature.
ASTM Standard Analysis

D2500 Manual
D5771 Optical detection Stepped Cooling Method
D5772 Linear Cooling Rate Method
D5773 Constant Cooling Rate Method
D7689 Mini Method
D2500: Cloud Point of Petroleum Products
1. Liquid column separation of thermometers occasionally occurs and may escape detection.
Thermometers should be checked periodically and used only if their ice points are 0 ± 1°C,
when the thermometer is immersed to the immersion line in an ice bath, and when the
emergent column temperature does not differ significantly from 21°C.
2. The disk, gasket, and the inside of the jacket must be kept clean and dry, otherwise this may
lead to frost formation, which may cause erroneous results.
3. Maintain the temperature of the cooling bath at 0 ± 1.5°C.
4. Report the cloud point to the nearest 1°C, at which any cloud is observed at the bottom of the
test jar, which is confirmed by continued cooling.
D5771: Cloud Point by Optical Detection Stepped Cooling Method

1. A wax cloud or haze is always noted at the bottom of the test jar where the temperature is
lowest. A slight haze throughout the entire specimen, which slowly becomes more apparent
as the temperature is lowered, is usually due to water in the specimen. Generally this water
haze will not interfere with the determination of the wax cloud point. In most cases of
interference, filtration through dry lint-free filter papers is sufficient.
2. Samples of very viscous materials may be warmed until they are reasonably fluid before they
are sampled. However, no sample should be heated more than absolutely necessary.
3. The sample shall not be heated above 70°C. When the sample is heated above 70°C, allow
the sample to cool below 70°C before filtering or inserting into the apparatus.
4. When moisture is present in the sample, remove moisture by a method such as filtration
thorough dry lint-free filter paper until the oil is perfectly clear. Make such filtration
at a temperature at least 14°C above the expected cloud point.
18
5. A test head simulator with a known resistance is used to calibrate the equipment.
D5772: Cloud Point by Linear Cooling Rate Method
thorough dry lint-free filter paper until the oil is perfectly clear. Make such filtration at a
temperature at least 14°C above the expected cloud point.
D5773: Cloud Point by Constant Cooling Rate Method
thorough dry lint-free filter paper until the oil is perfectly clear. Make such filtration at a
temperature at least 14°C above the expected cloud point.
D7689: Cloud Point by Mini Method
thorough dry lint-free filter paper until the oil is perfectly clear. Make such filtration
at a temperature at least 14°C above the expected cloud point.
4. Moisture will be noticed in the sample as a separate phase or as a haze throughout the entire
sample. Generally, a slight haze will not interfere with the detection of the wax cloud.
19
COLOR MEASUREMENT OF PETROLEUM PRODUCTS
There are several color scales for measuring color of petroleum products and lubricants. Since
they use numerically different scales, only the specified test method should be used for this
measurement.
D1500: ASTM COLOR SCALE

1. When an exact match is not found and the sample color falls between the two standard
colors, the higher of the two colors is reported.
2. In such case, report the result as L (darker glass), e.g., L7.5
3. Never report the color as being darker than a given standard, except when it is darker than 8,
e.g., D8.
4. Do not report the color than in 0.5 units.
DENSITY AND GRAVITY OF PETROLEUM PRODUCTS
There are several test methods for measuring density, specific gravity or API gravity of
petroleum products. Some are specific for a product; others can be applied to any petroleum
product.
D287: API Gravity of Crude Petroleum and Petroleum Products
1. The cylinder with the sample in it should be placed in a constant temperature bath to avoid
excessive temperature variation during the test.
2. Use hydrometers supplied with a calibration certificate.
3. Thermometers must be calibrated against a master thermometer at least once a year.
4. Any air bubbles formed after the sample is poured into the cylinder must be removed. Before
density measurements.
5. When analyzing viscous oils, allow sufficient time for the hydrometer to reach equilibrium.
6. Correct the observed hydrometer reading for the meniscus effect, the thermal glass expansion
effect, alternate calibration temperature effects, and reduced to the reference temperature by
means of the volume correction tables.
20
D1298: Density, Relative Density, or API Gravity of Crude

Petroleum and Liquid Petroleum Products by Hydrometer Method
1. The notes given for Test Method D287 above also apply to this test method.
D4052: Density, Relative Density, and API Gravity of Liquids by

Digital Density Meter
1. Do not use this method for samples so dark in color that the absence of air bubbles in sample
cell cannot be established with certainty.
2. Precise setting and control of the test temperature in the sample tube is extremely important.
An error of 0.1°C can result in a change in density of one in the fourth decimal place.
3. The density meter must be calibrated when first set up, and whenever the test temperature is
changed. During routine operation, calibrate weekly.
4. Air used for calibration must be pure and dry.
5. Calibration materials that may be used include: dry air, redistilled freshly boiled and cooled
reagent grade water, n-nonane, n-tridecane, cyclohexane, n-hexadecane.
6. If a major adjustment is required, it indicates needing for cleaning the deposits in the sample
tube. This can be achieved by washing the tube with warm chromic acid or surfactant
cleaning fluids.
7. Make sure that no bubbles are trapped in the tube, with the illumination light. The sample
must be homogenous and free of even the smallest bubbles.
D5002: Density and Relative Density of Crude Oil by Digital Density

Analyzer
1. The same notes as above for Test Method D4052 also apply to this test method.
ETHANOL AND METHANOL IN FUELS BY GC: D5501

1. This test method does not purport to identify all individual components common to ethanol
production or the fuel. Water cannot be determined by this test method and shall be
determined by a procedure such as Test Method D1364, and the results used to correct the
concentrations determined by this test method.
2. This test method is inappropriate for impurities that boil at temperatures higher than 225°C
or for impurities that cause poor or no response in a flame ionization detector, such as water.
21
3. In the apparatus used inadequate splitter, poor injection technique, and overloading the
column can result in poor resolution. Avoid overloading, particularly of the ethanol peak, and
eliminate this condition during analysis.
4. To minimize the loss of hydrocarbon light ends, chill the sample before transferring an
aliquot into an auto sampler vial. Seal immediately. Obtain the test sample for analysis
directly from the sealed auto sampler vial.
5. After installing the columns according to the manufacturer’s instructions, check the system
for leaks, and if found tighten or replace the fittings before proceeding.
6. Adjust the operating conditions of the gas chromatograph as given in Table 1 of the test
method, and allow the system to equilibrate.
7. The linearity of the gas chromatograph system shall be established prior to the sample
analysis.
8. Verify the linearity of the flame ionization detector as given in Practice E594.
9. Conduct a regular statistical quality assurance program monitoring both precision and
accuracy.
10. See Appendix X3 for guidance for factors that affect precision and accuracy of analysis
using this test method.
EVAPORATION LOSS OF LUBRICATING

OILS BY THE NOACK METHOD: D5800
There are three procedures under this designation: Procedure A (the original DIN method using
Wood’s metal), Procedure B (Non-Woods metal apparatus marketed by ISL / PAC), and
Procedure C (from Savant lab). A discussion of the evaporation loss methods by Noack
procedures can be found in: R. A. Nadkarni – “Engine Oil Volatility: Noack Evaporation
Methods”, J. ASTM International, 6(1), #101691 [2008].
1. Be sure to use the correct manometer fluid to fill the manometer. The density of the fluid is
critical and must be of the type designed for the manometer (See 6.11, Note 1). Millimeters
of water (implicitly at 1 G) is a unit of pressure. Not every manometer that gives readings in
mm of water is made for use with water as the manometer fluid. Consult the instrument
manual or manufacturer for the correct manometer fluid properties.
2. Be sure that the manometer reservoir is filled so that the manometer is reading exactly zero
with no external vacuum or pressure. This should be checked before each run. Evaporation
may require occasional refilling of the manometer reservoir. It is also important that the units
be properly leveled.
22
3. For inclined manometers, be sure to read the meniscus at the same position at both 1 and 20
mm of water.
4. Rubber tubes used for connections should be changed periodically because oil-mist causes
rubber swelling after extended period of service.
5. Cleaning at regular intervals of foreign material adhering on exhaust system parts,

particularly on Y-glass piece, is necessary.
6. There is a drop in the metal bath temperature when inserting the sample. Monitor that the
temperature recovers in approximately 3 min.
7. Strong air drafts or turbulence around the pressure transducer or the heated crucible may
adversely affect the test precision and accuracy. Do not place the instrument in a draft area;
however, the exhaust fumes from the evaporating oil shall be ventilated to an outside source.
A draft dodger assembly is described in the Appendix.
8. Clean the cover and the crucible thoroughly with solvent between tests and allow to dry.
Remove stubborn lacquer by immersing in hot detergent solution, by light abrasion with fine
carborundum powder, or a fine abrasive pad.
9. Vacuum must be accurately set and maintained or the Noack results can be greatly altered.
Run the pump for 30 min before testing. Vacuum pump should be cleaned out daily using a
hydrocarbon solvent. Consult the manufacturer for a compatible solvent recommendation.
Run a pressure test daily; let the vacuum run until the pressure stabilizes.
10. Condensed liquid collecting in tubes and at junctions is also a common source of problem.
11. The CEC Reference Oil RL-172 should be analyzed each day the samples are analyzed.
Make sure the correct reference oil performance certificate is being used. Some suppliers
may not be correctly updating their reference oil performance certificates. Note that the
evaporation loss values differ for Procedures A and B.
12. Cleanliness of the extraction tube, glass and silicone tubing, and air jets should be assured
prior to all testing.
13. Possible contamination of the thermal sensor well with slag and Woods metal should be
monitored. Slag should be checked and removed periodically after a series of runs.
14. Check all the connections to be sure they are tight before the test. Alignment of all
connections without any restrictions should be maintained. All tubing should allow all flow
to travel downhill to the vacuum pump (no low points).
15. Verify that the temperature probe holder spring is working properly to seat the probe
correctly. The temperature probe should be cleaned to remove varnish.
23
16. On automatic machines, if pressure reads different from zero before testing, recalibrate the
pressure.
17. If the extraction tube is loose, tighten or check the gasket.
18. Woods metal bath must be full and overflowing around the crucible and thermal sensor
wells.
19. At all times while handling the sample crucible, be careful not to splash the test sample on
the crucible lid, especially when removing the lid. Use of a table-mounted holder to hold the
crucible may help prevent splashing while operating the crucible. See section 20.10.
20. Do not overtighten the crucible lid, and do not use the extraction tube as a handle to tighten
or open the lid.
21. Timing—Place the crucible in the bath, connect the vacuum and start the timer in quick
succession, as nearly simultaneously as possible.
22. Start the pump before starting the stopwatch for the test. Instrument electronics must be on
for at least 30 min prior to the start of the first test to warm-up the vacuum transducer.
Leaving the electronics on overnight satisfies this recommendation.
23. Monitor the calibration thermometer versus recorded temperature occasionally during run.
The temperature circuit electronics should be verified at least monthly using a calibrated
temperature probe simulator.
24. End of Test—Disconnect vacuum at the end of the test time and place the crucible in cooling
bath within 1 min.
25. Be careful not to tilt the crucible in handling during the test, particularly at the end.
26. Final weighing should not be done until the crucible is at room temperature. Do not use extra
force (e.g., hammers) to open or close the crucible.
27. At the end of the test, check the pressure and temperature scans from automatic machines to
check that proper parameters were maintained during the runs.
28. Procedure C—Be sure that the thermocouple is touching the side of the reaction flask
bottom. This can be accomplished by looking down through the reaction flask top when
positioning the thermocouple.
29. To reduce potential flow problems, make certain that the hose from the unit to the exhaust
hood or vent is not pinched anywhere.
30. To prevent leaks, securely seat all glassware, the thermocouple sheath, and the orifice tube.
24
31. For accurate results, make certain that the test runs as close to 1 h as possible (within 15 sec).
32. At the end of the test, the glassware may be removed for the 20-min cool-down period using
thermal gloves. This permits immediate starting of another run with a second set of
glassware.
33. Alternatively, two sets of top and bottom flasks may be used each with its own orifice tube
and cap.
FLASH POINTS
There are several flash point methods in ASTM D02 Committee: D56 Tag Closed Cup, D92
Cleveland Open Cup (COC), D93 Pensky Martens Closed Cup (PMCC), D3828 Seta Closed
Cup. Flash point values are a function of the apparatus design, the condition of the apparatus
used, and the operational procedure carried out. Flash points therefore can only be defined in
terms of a standard test method, and no general valid correlation can be guaranteed between
results obtained by different test methods, or with test apparatus different from that specified.
An excellent reference on flash point is available in ASTM Manual 72 “The Practice of Flash
Point Determination: A Laboratory Resource” by E. D. White and R. G. Montemayor
[2013].
The flash point tests both D92 and D93 are susceptible to give erroneous results if the sample
integrity is not maintained. The limiting temperature of 62°C distinguishes between the
flammable and the combustible material per the U.S. Department of Transportation regulation.
Hence, a slightly false lower temperature can result in the material being classified as flammable
with attendant extra shipping precautions and costs. Information is summarized below which if
appropriately followed should result in reliable flash point results in a laboratory.
1. When precautions are not taken to avoid the loss of volatile materials erroneously high flash
points can be obtained. Do not store the samples in plastic containers, since the volatile
material may diffuse through the container walls. Do not open the containers unnecessarily.
Do not transfer between the containers unless the sample temperature is at least 20°F (11°C)
below the expected flash point. Further, the containers should be capped at all times except
when taking a specimen for analysis. When possible, the flash point should be the first
analysis made on the sample received in the lab.
2. Do not store the samples in gas-permeable containers since volatile material may diffuse
through the walls of the enclosure. Samples in the leaky containers are suspect and should
not be used for valid results.
3. When possible, flash point should be the first test performed on a sample, and the sample
should be stored at low temperature. Typical sample storage temperature is normal room
temperature or lower.
25
4. The flash point is considered the stage where a large flame appears and
instantaneously propagates itself over the entire surface of the test specimen. Do not confuse
the true flash point with a blue halo or an enlarged flame which sometimes occurs especially
with halogenated hydrocarbons and admixtures on application of the flame.
5. Samples containing dissolved or free water can be dehydrated with calcium chloride or by
filtering through a qualitative filter paper or a loose plug of dry absorbent cotton, before flash
point measurement.
6. Thermometer (or other temperature measuring device) must be properly calibrated. Check it
against a master thermometer at least once a year. In the interim, use ice point method for
calibration.
7. Erroneous flash points will result if air bubbles or foam collected on the top of the sample are
not eliminated.
8. When using a gas flame as the ignition source, meticulous attention needs to be paid to the
details relating to the test flame application, test flame size, rate of temperature increase, and
rate of passing the test flame over the sample tom obtain good results.
9. There should be no draft in the place near the flash point tester. Tests made in a lab hood or
in any location where draft occurs are not reliable. A draft shield is recommended to prevent
drafts from disturbing the vapors above the test cup. This shield should cover at least three
sides of the test cup vicinity. If the instrument is kept in a fume hood, turn the air-flow off
during testing. Particularly during the last 17°C (30°F) for COC (D92) rise in temperature
prior to the flash point, take care to avoid disturbing the vapors in the test cup by careless
movements or breathing near the cup. Use of a three-sided shield is recommended.
10. If the test must be done in a lab hood for safety reasons, turn the draft off or reduce it to
minimize the air currents over the test cup during ignition source application period or use a
shield of suitable size with an open front to prevent drafts from disturbing the vapors above
the test cup.
11. Thoroughly clean and dry all parts of the test cup. Be sure that any residual cleaning solvent
is removed. The cleaning solvents used must be capable of thoroughly removing the residual
samples in the cup.
12. Heat viscous samples until they are reasonably fluid before being poured into the cup.
However, the temperature during heating must not exceed 56°C (100°F) for COC and 17°C
(30°F) for PMCC below the probable flash point.
13. For very viscous materials, heat them in the original container at a temperature not exceeding
28°C below the expected flash point for 30 minutes. If not completely liquefied, heat for
another 30 minutes. Do not transfer the liquid sample to a sample cup unless it’s temperature
is more than 18°C below its expected flash point.
26
14. The flash point obtained needs to be corrected for barometric pressure. Do NOT use a
aneroid barometer such as those used at weather stations and airports.
14a. Correct the observed flash point for ambient barometric pressure, if it is different from
101.3 kPa or 760 mm of mercury. The necessary equation is given in the method.
Unless there is severe atmospheric disturbance it is possible that this correction may be
very small.
14b. Do not use the barometric pressure obtained from weather reports or radio broadcasts.
These use aneroid barometers and are pre-corrected to give sea-level readings. Using
them will give erroneous correction factors. Consult D3631 for the proper set-up and
the use of the barometers.
15. Corrected flash point should be rounded to the nearest 1°C (2°F). Never report a fractional
flash point.
16. Verify the performance of the manual or the automated apparatus at least once per year by
determining the flash point of a certified reference material such as those issued by NIST.
More frequent checking with a secondary working standard is recommended once the
primary certified reference material gives satisfactory results.
17. When the flash point of the standards obtained is not within the certification limits, check the
condition and operation of the apparatus to ensure conformity with the details listed in the
STM, especially in regards to the position of the temperature measuring device, the
application of the test flame, and the heating rate.
18. Meticulous attention to all details relating to the test flame application, test flame size, rate of
temperature increase, and rate of passing the test flame over the sample must be given to
obtain good results.
D56: Flash Point by Tag Closed Cup Tester
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 below the expected flash point. Where possible, flash
point shall be the first test performed on a sample and the sample must be stored at low
temperature.
2. Verify the performance of the apparatus at least once per year by determining the flash point
of a certified reference material such as those listed in Annex A2 of this standard.
3. Observed flash point obtained must be corrected for barometric pressure.

27
4. Once the performance of the apparatus has been verified, the flash point of a secondary
working standard can be determined along with their control limits. These secondary
materials can then be utilized for more frequent performance checks.
5. Never make a repeat test on the same specimen of the sample; always take a fresh specimen
of sample for each test.
D92: Flash And Fire Points by Cleveland Open Cup Tester
1. This test method is valid for petroleum products with flash points above 79°C and below
400°C except fuel oils.
determining the flash point of a certified reference material such as those issued by NIST.
3. More frequent checking with a secondary working standard is recommended once the
primary certified reference material gives satisfactory results.
aneroid barometer such as those used at weather stations and airports. These are precorrected
to give sea level readings and would not give the correct readings for this test.
D93: Flash Point by Pensky-Martens Closed Cup Tester
1. This test method is valid for flash point determination of petroleum products in the
temperature range 40 to 370°C, and of biodiesel in the temperature range of 60 to 190°C.
2. Procedure A is applicable to distillate fuels, new and used lubricating oils; procedure B is
applicable to residual fuel oils, and other miscellaneous products; and procedure C is
applicable to biodiesel (B100). Only automated apparatus must be used for procedure C. For
heavy and viscous samples use procedure B. The procedure A uses slow stirring and fast
heating; The procedure B uses rapid stirring and slow heating. Using Procedure A for high
viscosity samples will result in erroneous low flash points.
3. Automated apparatus must follow the requirements of manual apparatus, such as:
- The temperature of the specimen in the test cup must be at least 18°C below the
expected flash point.
- The stirring rate must be 250 ± 10 rpm.
- The heating rate must be 1 to 1.6°C/min.
28
4. Temperature measuring devices could be thermometer or electronic. If a thermometer is

used, check that it has the correct required ASTM designation. The thermometer or the
temperature measuring device must be calibrated on a regular basis. Check them against a
master thermometer at least once a year. In the interim, use ice point method for calibration.
5. Thoroughly clean and dry all parts of the test cup. The cleaning solvent used must be capable
of thoroughly removing the residual samples in the cup. Be sure that any residual cleaning
solvent is removed.
determining the flash point of a certified reference material such as those issued by NIST. At
least annually analyze a NIST Certified Reference Material (CRM) reasonably close to the
temperature range of the sample.
29
NIST CRM MATERIAL FLASH POINT, °C

8517 n-Decane 52.8 ± 2.3
8518 n-Undecane 68.7 ± 3.0
8519 n-Tetradecane 109.3 ± 4.8
8520 n-Hexadecane 133.9 ± 5.9
(These ± limits are different from those given in the NIST certificates).
7. More frequent checking with a secondary working standard is recommended once the
primary certified reference material gives satisfactory results. Each day the samples are
analyzed, analyze a Secondary Working Standard (SWS), e.g., Aldrich high purity n-
hexadecane. Plot this data on a quality control chart. Take prompt remedial action when the
chart indicates out-of-control situation.
8. If the CRM or SWS results are not in control, check the condition of the operation of the
instrument. After any adjustment, repeat the CRM and/or SWS analysis.
aneroid barometer such as those used at weather stations and airports.
9a. Correct the observed flash point for ambient barometric pressure, if it is different from
101.3 kPa or 760 mm of mercury. The necessary equation is given in the method. Unless
there is severe atmospheric disturbance it is possible that this correction may be very
small.
9b. Do not use the barometric pressure obtained from weather reports or radio broadcasts.
These use aneroid barometers and are pre-corrected to give sea-level readings. Using
them will give erroneous correction factors. Consult D3631 for the proper set-up and the
use of the barometers.
10. After correcting for barometric pressure, round the temperature to the nearest 0.5°C, and
report.
D3828: Flash Point by Seta Small Scale Closed Cup Tester
1. This test method is valid for flash point determination of petroleum products and biodiesel
liquid fuels. Method A gives flash/No flash results while Method B gives the actual
numerical flash point result.
2. The temperature measuring device as well as the flash point apparatus should be checked for
performance at least once a year by determining the flash point of a certified reference
material such as those issued by NIST.
3. More frequent checking with a secondary working standard

is recommended once the primary certified reference material gives satisfactory results.
30
aneroid barometer such as those used at weather stations and airports. These are precorrected
to give sea level readings and would not give the correct readings for this test.
Foaming Characteristics of Lubricating Oils: D892

1. This test has poor precision; hence, it is imperative that the test be performed exactly as
written. Further discussion about this test can be found in a review “Foam Tests for
Lubricating Oils: Limitations of Reliability and Reproducibility” by R. A. Nadkarni in
J. ASTM International, 6 (7), # 102106 [2009].
2. Norton stone diffusers are known to be very unreliable regarding their porosity and
permeability; hence, new stones (and metal diffusers) must be checked as per Annex A1 in
the standard. Out-of-specification diffusers are a major source of inaccuracy in this test
method.
3. Avoid touching the clean diffusers with one’s hands.
4. Gas diffusers permeability and porosity can change during use; therefore, it is recommended
that they must be checked when new and periodically thereafter for porosity and
permeability, depending on usage; once a week checking is recommended.
5. Check the connection between the gas diffusers and air inlet tubes is air-tight.
6. Inlet air must be dried by passing through a desiccant drying tower. Change the desiccant
when it begins to show presence of moisture by changing color from blue to pink.
7. Total volume of the air leaving the apparatus must be measured.
8. Check the thermometer calibration at least once a year against a master thermometer. For
other temperature sensing devices, checking the calibration at least once a year against a
traceable source is recommended.
9. Thorough cleansing of the test cylinder and air inlet tube is essential after each use to remove
any residual additive from previous analysis.
9a. Cylinders are cleaned with petroleum distillate, petroleum spirit, clean dry air, distilled
water, acetone, and clean air in sequence.
9b. Gas diffusers are cleaned five times with petroleum distillate, toluene, petroleum spirit,
and clean dry air in sequence.
10. Oil or water baths must be used to control the testing temperature (even 75°F) within ±1°F
for sequences I and III, and within ±2°F for sequence III.
31
11. In sections 10.2 – 10.4, verify that the sample has reached the bath temperature before
starting the foam measurements.
12. In section 6.1, verify the distance between inside bottom of the cylinder and the 1000 mL
graduation mark.
13. In section 6.1, a diffuser centering washer is used to ensure that the diffuser head is centered
within the cylinder to eliminate wall interference with foam generation and expansion during
and after the blowing period. This is particularly helpful when dark fluids are tested or
lighting conditions or darkened bath liquids make centering difficult.
14. In section 6.1, hold the cylinders in a upright position by use of a suitable device. If the
cylinders are not vertical or move during the test, or both, foam levels errors can be
increased.
15. Total volume of air passing through the system must be measured at exit (470 ± 25 mL).
Without this step there is no way of ascertaining that the system is air tight.
16. Flow meters must be correctly calibrated and the flow rate must be carefully controlled.
17. Stopwatches must be calibrated against a national standard at least once a year. Annex A3
(Timer Accuracy) in Test Method D445 is a good source for guidance on how to check the
timers for accuracy.
18. If using Option A, all entrained air bubbles after stirring must be dispersed before testing.
19. It is misleading and inappropriate to apply Option A for quality control of freshly made
blends or comparing/reporting Option A as regular foam test results.
20. If the alternative procedure is used for foam measurements, the data should not be reported as
obtained by Test Method D892, without stipulating that it was by using alternate procedure.
GUM CONTENT OF FUELS BY JET EVAPORATION: D381
1. Do not use a desiccant in the cooling vessel such as a desiccator. It could lead to erroneous
results.
2. The beakers etc. used in this analysis for weighing gum should only be handled with stainless
steel forceps or tongs.
3. Air used must be filtered. Steam supply should be free of oily residue.
4. Calibrate the air flow to ensure all outlets meet the 600 ± 90 mL/s air flow requirement.
Verify the steam flow to ensure all outlets meet the 1000 ± 150 mL/s steam flow
requirement.
32
5. After three extractions of the residue with heptane, no further extractions are to be
performed, since portions of insoluble gum may be removed due to mechanical action, which
could lead to lower solvent washed gum content being determined.
KINEMATIC VISCOSITY : D445

Kinematic viscosity is one of the most precise and most widely used test methods by the D02
Committee on Petroleum Products and Lubricants laboratories. The test needs calibration or
verifications of various components of the analytical system: temperature measuring devices,
constant temperature baths, timers, viscosity tubes. Calibration of various system components is
critical in obtaining accurate and precise results using this method.
Temperature Measurement—Temperature control is perhaps the single most important parameter

in obtaining accurate and precise kinematic viscosity results.
1. The bath temperature must be controlled within ± 0.02°C in the range from 15 to 100°C. For
temperatures outside this range, the variation must not exceed ± 0.05°C.
2. Correct thermometers must be used as specified in the standard: ASTM 120C for 40°C and
ASTM 121C for 100°C measurements.
3. Use a magnifying lens (X 5) to read the thermometer, since it is difficult to read to 0.01°C
difference.
4. Thermometers or other temperature measuring devices must be accurate within ±0.02°C.

They should be calibrated or verified against a standard thermometer at least semiannually.
Do the ice point determination every six months between full calibrations. New
thermometers should be checked monthly at least for the first six months of use.
5. Use of two thermometers per bath is recommended. Two readings should agree within
0.04°C of each other.
6. Thermometers shall be held in an upright position under the same conditions of immersion as
when calibrated. In order to obtain the most reliable temperature measurement, it is
recommended to use two thermometers with valid calibration certificates be used. They
should be viewed with a lens assembly giving approximately five times magnification and be
arranged to eliminate parallax errors. The difference between the two thermometers should
be within ±0.04°C.
Constant Temperature Bath:
1. The constant temperature bath should not be kept in a draft area. A strong draft such as
caused by placing the bath in a fume hood will degrade the temperature uniformity of the
bath.
33
2. The hydrocarbon oil in the bath must be changed well before it starts discoloring due to
oxidation and degradation.
3. The oil sample in the viscometer must be at least 20 mm below the surface of the bath and at
least 20 mm above the bottom of the bath.
3a. The samples should be equilibrated in the bath for about 30 min before taking
measurements.
4. Never add or withdraw a viscometer while any other viscometer is in use for measuring a
flow time.
Timers:
1. Stopwatch must be accurate within 0.07 % and should have a resolution of 0.1 sec or better.
They must be calibrated or verified against a radio time signal at least annually. NIST
provides such phone service. Do not use electric timers plugged into the AC mains. They can
fluctuate in their frequency control.
2. A well-illuminated area will help in accurately detecting the meniscus as it crosses the timing
line.
Viscometers:
1. The most common sources of error are caused by dust particles lodged in the capillary bore
and temperature measurement errors.
2. Use the correct type of viscometer depending upon the viscosity of the sample as given in
Table 1 of Test Method D445.
3. Viscometer must be calibrated when purchased and then periodically checked with viscosity
oil standards. They can be calibrated against a master viscometer. Calibration constant should
be expressed to the nearest 0.1 % of its value.
4. Viscometers must be kept in a vertically mounted within 1° position in all directions. Use a
bubble level on the top of the bath to check this. The entire length of the viscometer must be
maintained at the correct temperature of measurement.
5. Cannon viscosity oil standards have an expiry date on them. Cannon suggests that the oil
standards can be used up to one year beyond the expiry data, if the bottle has not been
opened. Do not use beyond that date.
5a. The values for calibration standards should be within ±0.35 % of their certified values.
5b. According to Cannon, the easiest way to check that the correct calibration factor is being
used for a viscometer is to run the same sample in two different viscometers located next
34
to each other in the same bath at the same time. The results should be within 0.3 % of
each other.
6. The flow time of a sample between the marks on a viscometer must not be less than 200 sec.
If so, use a different tube.
6a. There should be sufficient illumination to enable consistent visual detection of the
meniscus crossing the timing line.
7. Properly cleaning of viscometer tubes is extremely important, particularly when analyzing

used oils. Thoroughly clean the viscometers between successive determinations with sample
solvent (e.g., naphtha), drying solvent (e.g., acetone), and dry air for two minutes. These
solvents should be filtered before use. Also, periodically clean the viscometer with chromic
acid or other non-chromium containing strongly oxidizing cleaning solutions.
7a. Exposure to caustic samples or cleaning materials will cause the viscometer constant to
change even with a minimal exposure to such materials.
8. Some silicone fluids, waxy and highly polar samples can be very difficult to fully remove
from a viscometer. Use of chromic acid or other oxidizing cleaner is necessary in such cases.
9. Each viscosity measurement must be done twice, and the average value used if the two
measurements agree within 0.2%. If not, repeat the determination after thorough cleaning and
drying of the viscometers and filtering of the sample.
10. Averages of two measurements have to be used in the calculations.

Use correct flow time and calibration factor for the particular tube used in the calculations.
11. Report the kinematic viscosity results to four significant figures.
DYNAMIC VISCOSITY AND DENSITY BY STABINGER

VISCOMETER: D7042
1. For samples that are likely to contain particles (e.g., used oils or crude oils) pass the sample
through a 75 µm screen to remove the particles. For removal filings, use of a magnet is
appropriate. Waxy samples must be heated to dissolve the wax crystals prior to filtration and
a preheater filter shall be used.
2. If required, mix the sample to homogenize. Mixing at room temperature in an open container
can result in the loss of volatile material. Mixing in closed, pressurized containers, or at sub-
ambient temperatures is recommended.
3. For waxy or other samples with a high pour point, before drawing the test specimen, heat the
laboratory sample to the desired test temperature, which has to be high enough to dissolve the
wax crystals.
35
4. Use only a calibrated apparatus as described in Section 6 of the test method. The calibration
shall be checked periodically using certified reference standards as described in Section 9 of
the test method. The recommended interval for viscosity and density calibration is once a
month, and for temperature control once a year.
KINEMATIC VISCOSITY OF USED OILS BY HOUILLON

VISCOMETER: D7279
Discusssion of Houillon kinematic viscosity determination can be found in R.A. Nadkarni and
J. L. lane – “Determination of Kinematic Viscosity of Used Lubricating Oils Using Houillon
Viscometer”, in J. ASTM International, 8 (7), # 103138 [2011].
1. Thermometers or other thermometric devices should have an accuracy of better than ±

0.02°C. Calibrate at least once a year against a standard thermometer.
2. Any timing device used should have an accuracy within ±0.07 %. Calibrate or verify against
a national time signal at least annually.
3. The most common sources of error are caused by particles of dust lodged in the capillary
bore of the viscosity tube (particularly for used oils) and temperature measurement errors.
Modification of the cleaning constants by increasing the number of cycles and increasing the
aspiration time before and after passage of the solvent (See Section 11) may be required.
4. Use a volume delivery device that can introduce the entire specimen volume in one
operation.
36
ANALYSIS OF BARIUM, CALCIUM, MAGNESIUM, AND ZINC

IN UNUSED LUBRICATING OILS BY ATOMIC ABSORPTION
SPECTROMETRY: D4628
1. Many lubricating oils contain viscosity index (VI) improvers and may give low results when
calibrations are performed using calibration standards that do not contain the VI improvers.
1a. The VI improver effect may be eliminated by using either a very large sample dilution or
by adding the same VI improver to the calibration standards. The latter approach would
usually be impractical since for unknown samples, the laboratory would not know the
type or the concentration of the VI improver present, if any.
2. Standardize the instrument each time the flame is ignited. Calibration must be carried out
prior to each group of samples to be analyzed, and after any change in instrumental
conditions, as variation occurs in the instrument behavior. Readings may also vary over short
period of times from such causes as buildup of deposits on the burner slot or in the nebulizer.
3. A single standard should be aspirated from time to time during a series of samples to check
whether the calibration has changed. A check after every fifth sample is recommended.
4. The visual appearance of the flame serves as a useful check to detect changes of condition.
5. Low level working calibration standards should be prepared fresh daily from higher
concentration (e.g., 500 or 1000 mg/kg) stock solutions.
6. Always run a blank with all solvents and other reagents added to the standards and the
samples.
7. Whenever possible, background subtraction must be employed to obtain more reliable

results.
8. To avoid flame transport problems, add a metal free base oil of about 4 cSt @ 100°C to both
samples and calibration standards. A 100 neutral base oil is suitable. Avoid highly paraffinic
oils.
9. Standard addition technique may be employed for samples known to have elemental or other
interferences.
10. For best results, use a bracketing technique for calibration. This involves taking absorbance
readings for the calibration solutions before and after each of the sample solutions.
11. Employ adequate mixing and sampling procedures especially for heavy oils. Heat heavy oils
sufficiently to obtain good liquidity and then shake vigorously on a shaking machine.
37
12. Use the analytical wavelength specified in the methods for measurements, because they have
been established by experiment to be the optimum wavelengths and free from spectral
interferences.
13. Disassemble and clean the burner on a maintenance schedule that is appropriate to frequency
and type of use.
14. Inspect the nebulizer tubing daily for kinks or cracks, and replace as necessary.
15. Measure the nebulizer uptake rate daily, to check for plugging. Clean it if the rate is not
normal.
16. Adjust for variations due to build-up of deposits on the burner or the nebulizer during the
course of determinations by frequently nebulizing the check standard.
17. Adjust the gas flow rates when using the nitrous oxide/acetylene flame to minimize the
carbon buildup on the burner. Clean off the carbon regularly during analysis with a sharp
instrument. Carbon buildup can be particularly troublesome when nebulizing the organic
solutions.
18. Prevent leakage of acetone from the acetylene gas tank by monitoring the pressure. Replace
the tank when the pressure reaches 50 psi.
19. Check the alignment of the hollow cathode lamps before analysis, following the
manufacturer’s instructions.
20. Clean all apparatus, glassware, etc. to prevent contamination. Soak the glassware in warm
dilute (5%) nitric acid for several hours and then rinse thoroughly with deionized water.
21. Verify the linearity of the concentrations/absorbance response for each analyte following the
instrument manufacturer’s instructions. Perform all determinations within this range. Prepare
the standard solutions with concentrations at the top of the linear range.
22. Match the matrix of standard solutions to sample solutions as closely as possible.
23. Use pure, analyte-free solvents. D4628 method recommends Baker “kerosene” (deodorized).
Verify that the solvents are free of the analyte.
24. Add ionization suppressant to all applicable solutions (standards and samples) at the
recommended concentration as a guide. Determine the “right” concentration by experiment
using the instructions in the method. Add the same concentration of ionization suppressant to
all standard and sample solutions, and maintain these concentrations when the solutions are
diluted.
25. Keep all absorbances within the linear and calibration ranges. Dilute the sample solutions
gravimetrically, if necessary.
38
26. Since checking the absorbance of a sample is very quick once the instrument is calibrated,
but changing the wavelength settings and hollow cathode lamps takes longer time, it is most
economical to make measurements at a single wavelength on a series of samples and
standards before changing conditions for a different analyte measurement.
LEAD IN GASOLINE BY AAS: D3237

1. Employ adequate mixing and sampling procedures.
2. Use the analytical wavelengths specified in the method for measurements, because they have
interferences.
3. Dissemble and clean the burner on a maintenance schedule that is appropriate to frequency
and type of use.
4. Inspect the nebulizer tubing daily, for kinks, restrictions, or cracks, and replace if necessary.
5. Measure the nebulizer uptake rate daily, to check for plugging. Clean, if the rate is not
normal.
6. Standardize the instrument each time the flame is ignited.
7. Adjust for variations due to build-up of deposits on the burner or nebulizer during the course
of determinations by frequently nebulizing the “check” standard.
8. Adjust the gas flow rates when using the nitrous oxide/acetylene flame to minimize carbon
build-up on the burner. Clean off the carbon regularly during analysis with a carbon rod.
Carbon build-up can be particularly troublesome when nebulizing organic solutions.
9. Observe the visual appearance of the flame during analysis to note any changes in conditions.
12. Clean all glassware, etc. to prevent contamination. Soak glassware in warm dilute (5%) nitric
acid for several hours, and then rinse thoroughly with deionized water.
13. When analyzing trace amounts of analyte, dedicate all glassware for the exclusive use in a
specific test to avoid contamination.
14. Establish the frequency of preparation of stock standards by experiment. Keep these
39
standards refrigerated if necessary.
15. Prepare fresh working and check standards just prior to a set of determinations, and discard
after use.
16. Verify the linearity of the concentration/absorbance response for the analyte following the
instrument manufacturer’s instructions. Perform all measurements within this range. Prepare
17. Match the matrix of the standard solutions to sample solutions as closely as possible.
18. Prepare and run blanks that contain all solvents and other reagents added to the standard and
samples.
19. Calibrate the instrument prior to the analysis of each group of samples. For best results use a
bracketing technique for calibration.
20. Run appropriate check standards (quality control standards) periodically within the analysis
of a batch of samples (e.g., after every 5th determination). Recalibrate if the analyte
concentration changes by more than 5% relative to the previous check.
21. Use NIST set of lead in gasoline Standard Reference Materials periodically to check the
accuracy of the lab operation.
TRACE METALS IN GAS TURBINE FUELS BY AAS

AND FES: D3605
interferences.
and type of use.
normal.
40
12. Clean all glassware, etc. to prevent contamination. Soak glassware in warm dilute (5 %)
nitric acid for several hours, and then rinse thoroughly with deionized water.
after use.
samples.
concentration changes by more than 5 % relative to the previous check.
MANGANESE IN GASOLINE BY AAS: D3831

41
interferences.
and type of use.
normal.
12. Record the data and check these absorbances for linearity. If nonlinear, adjust the sample or
acetylene flow rates, or both, slightly to leaner conditions and repeat the calibrations until the
absorbances are linear. Rotation of the burner head to decrease the absorbance may aid in
achieving linearity.
after use.
42
samples.
TRACE METALS IN PETROLEUM COKE BY AAS: D5056

interferences.
3. When using multi-element hollow cathode lamps, spectral interferences can occur.
and type of use.
normal.
43
standards refrigerated if necessary. The method suggests preparing the standards daily.
after use.
samples.
23. Since this method uses ashing for sample preparation, work in a well-ventilated hood and use
adequate protection.
24. Prevent contamination from the muffle furnace by properly covering the sample containers.
Inspect the condition of the heating elements periodically. If surface flaking is observed,
replace the heating elements.
25. The ideal fusion after cooling will look like a clear glass inside the platinum dish. An opaque
44
melt indicates poor fusion and some of the ash may remain insoluble during the dissolution
step.
26. During dissolution of the melt in the solution, maintain constant stirring; otherwise some of
the ash constituents may precipitate, primarily, hydrous silica, due to heating the highly
acidic solutions. If this occurs, it is necessary to repeat the analysis.
Ni, V, Fe, AND Na IN CRUDES AND FUEL OILS BY AAS: D5863

1. Employ adequate mixing and sampling procedures. Use paint mixer for mixing heavy oil
samples. Heat heavy oils sufficiently to obtain good fluidity and then shake vigorously.
interferences.
3. When using multi-element hollow cathode lamps, spectral interferences can occur.
and type of use.
normal.
45
after use.
samples.
concentration changes by more than 5% relative to the previous check.
23. Since this method uses ashing for sample preparation, work in a well-ventilated hood and use
adequate protection.
ADDITIVE ELEMENTS IN LUBE OILS BY ICPAES: D4951
1. Check the temperature control of the ICP and ensure stable environmental conditions. This
can include temperature control of the spray chamber.
2. Employ adequate mixing and sampling procedures. Ultrasonic homogenizers and vortex
mixers are recommended.
46
3. Use the analytical wavelengths and background correction option specified in the test
method. When there is a choice of analytical wavelengths, choose sensitive lines. Ensure that
the selected lines are not subject to spectral interferences.
4. When spectral interferences cannot be avoided, determine and implement accurate

interference correction factors.
5. When sulfur is to be determined, be apprised that many commercially available standards

contain non-certified levels of sulfur. Separate sulfur standards can be advantageous.
6. When preparing multi-element standards, ensure that the various reagents are mutually
soluble.
7. Before use, check the accuracy of element concentrations of commercially obtained

standards. Either compare with alternative sources or analyze by independent methods.
8. Ensure that all glassware, etc. that contacts samples and standards does not contaminate
them.
9. Select solvents and other reagents that do not contain significant levels of analytes.
Wavelength scanning can indicate contaminated reagents.
10. By experiment, determine the frequency of standards preparation. Then, prepare fresh, as
needed.
11. Periodically, as needed, determine the linearity of the calibration curves. Perform quantitative
analyses with linear curves only.
12. Inspect the torch for cracks. Discard defective torches.
13. Use clean torches that do not have carbon accumulation.
14. After initially igniting the plasma, allow the instrument to warm up a minimum 30 min.
15. Inspect the peristaltic pump tubing daily, and replace deteriorating tubing. Daily replacement
is recommended.
16. Prepare and analyze reagent blanks. When blank values are significant, correct for the blank
or select alternative reagents that give insignificant blank values.
17. To minimize memory effects, allow sufficient solvent rinse time (minimally, 60 s) between
determinations.
18. Report results using the number of significant figures specified in the test method.
19. Dilute the standard oils and sample oils by the same factor. This factor shall be in the range
47
specified by the test method.
20. Implement internal standardization specified by the test method.
21. When carbon build-up in the torch is problematic, adjust experimental conditions to
eliminate the problem. Such adjustments can include: (1) reducing the sample uptake rate, (2)
increasing the intermediate argon gas flow rate, (3) use a jacketed, chilled spray chamber, (4)
lowering the torch, relative to the RF load coil.
ALUMINUM AND SILICON IN FUEL OILS BY ASHING,

FUSION, INDUCTIVELY COUPLED PLASMA ATOMIC
EMISSION SPECTROMETRY, AND ATOMIC ABSORPTION
SPECTROMETRY: D5184
1. It is extremely important to homogenize the fuel oil in the sample container to obtain a
representative specimen. Otherwise it can lead to erroneous results.
2. If the specimen contains considerable amount of moisture, foaming and frothing can cause
loss of material. In such cases discard the specimen, and to a fresh specimen add 1 to 2 mL of
2-propanol or 10 mL of 1:1 mixture of toluene and 2-propanol.
2a. Slowly raise the temperatures of heavy oils and crude oils that are known to contain
significant quantities of water to prevent these samples from foaming and spraying oil
and acid in the hood during decomposition.
3. Work in a well-ventilated hood and use adequate protection as prescribed in the appropriate
safety practices.
5. Prepare blank by carrying reagents used in the decomposition and preparation of samples
through the entire procedure.
6. Care for all apparatus and glass ware, etc. in accordance with good laboratory practice. Use
platinum tipped tongs to handle platinum ware.
6a. Soak all glassware in warm, dilute (5 %) nitric acid for several hours and then rinse
thoroughly with deionized water.
6b. Clean platinum ware by boiling in dilute (5 %) hydrochloric acid and rinsing thoroughly
with deionized water.
7. Discard the glassware that shows cracks and etching.

48
8. Keep the prepared test solution in plastic bottles since the solution contains fluoboric acid
and on prolonged exposure may attack the glass container.
9. Inspect torches before use for cracks and discard or repair as appropriate.
10. Use clean torches that are free of carbon build-up.
11. Replace or clean the load coil if oxidation is observed.
12. Allow the instrument to warm-up for at least 30 minutes or longer as suggested by the
manufacturer.
13. Visually inspect the peristaltic pump tubing daily for cracks, and replace if defective. Verify
the uptake rates daily.
14. Run the blank and appropriate check standard after every 5th sample or every 30 minutes.
Recalibrate if the net intensity of the standard changes by more than 5% relative to the
previous check.
15. Allow sufficient rinse time (not less than 60 seconds) between measurements to avoid
memory effects. Memory effects are present if a steady instead of an abrupt decrease in
signal is observed from taking multiple measurements.
16. Check the temperature and humidity controls of the laboratory containing the ICPAES
instruments and verify adequacy for performing accurate and precise analyses. Ensure that
stable environmental conditions exist throughout the period of use.
17. Check the accuracy of elemental concentrations of commercially obtained calibration

standards before use, either by comparing against suitable primary standards, or by an
independent analytical method.
18. Verify the absence of analytes in all solvents and reagents used, by performing a wavelength
scan. The net intensity should be zero.
19. Establish the preparation frequency of calibration standards by experiment. Prepare fresh
working and check standards before each set of measurements or daily as appropriate.
20. Check the linearity of the calibration curve of each analyte every 3 months or more
frequently.
49
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): D5185
1. It is extremely important to homogenize the used oil in the sample container to obtain a
representative specimen. Otherwise it can lead to erroneous results.
1a. Ultrasonic homogenization is preferred, but vortex homogenization can be used as an

alternative.

5. Establish the preparation frequency of calibration standards by experiment. It may be

necessary to prepare fresh working standards before each set of measurements or daily as
appropriate.
6. Check the linearity of the calibration curve of each analyte every time the analysis is carried
out by running a check standard independent of the calibration standard.
manufacturer.
12. Run the blank and appropriate check standard after every 5th sample. Recalibrate if the net
intensity of the standard changes by more than 5 % relative to the previous check.
50
14. Use the peak and background wavelengths suggested in the method, if possible. When there
is a choice, such as with sequential instruments, choose the wavelengths that will yield
signals of 100 to 1000 times the detection limit. Also, ensure that the chosen wavelengths
will not be interfered with from unexpected elements. See the section on interferences in the
method.
15. Check for spectral interferences and develop the necessary correction factors. Avoid spectral
interferences where possible by judicious choice of wavelength or by comparing the results
of 2 different wavelengths for the same element.
16. If sulfur is to be determined, do not use commercially available standards that contain
sulfonates. Prepare separate standards with known concentration of sulfur.
17. Ensure that elements will not react with one another resulting in insoluble compounds, when
preparing multi-element standards.
18. When analyzing used oils, use a high-solids Babington type nebulizer to avoid plugging
problems.
19. Dilute the sample and standards as much as possible to minimize nebulizer transport effects
caused by high viscosity oils or viscosity improvers and additives in the oil, and to reduce
potential spectral interferences. Both standard and sample solutions should not contain more
than 10 mass % oil.
20. Ensure that the standard solutions contain the same mass % oil as sample solutions. Maintain
the correct amount of oil by adding analyte-free base oil. Maintain consistent oil to solvent
ratio when diluting.
21. The internal standard procedure described in the method must be used to eliminate nebulizer
transport effects. Add the same exact concentration of internal standard element to all
samples and standard solutions.
22. Check for carbon build-up on the torch while nebulizing the working standard. Make the
necessary adjustments to eliminate build-up. These adjustments may consist of the following:
- Reducing the pump rate

- Increasing the auxiliary gas flow
- Using a chilled spray chamber
- Diluting the sample
- Making other adjustments described in the instrument manual
51
23. Differences in the viscosities of the test specimen solutions and standard solutions can cause
differences in the uptake rates adversely affecting the accuracy of the analysis. These effects
can be minimized by using a peristaltic pump or use of an internal standard.
24. Presence of particulates in the samples can plug the nebulizer causing low results. Use of a
Babington type high solids nebulizer helps to minimize this effect.
25. Use of a peristaltic pump is strongly recommended to provide a constant flow of the solution.
26. Use a base oil that is free of analytes and having a viscosity at room temperature as close as
possible to that of the sample to be analyzed.
27. Although the method allows the use of an internal standard as optional, it is strongly
recommended that this option be used. The companion method D 4951 makes the use of
internal standard mandatory.
TRACE METALS IN PETROLEUM COKE BY INDUCTIVELY

COUPLED PLASMA ATOMIC EMISSION SPECTROMETRY
(ICP-AES): D5600
safety practices.
3. Prepare blank by carrying reagents used in the decomposition and preparation of samples
through the entire procedure.
4. Care for all apparatus and glass ware, etc. in accordance with good laboratory practice. Use
platinum tipped tongs to handle platinum ware.
4a. Soak all glassware in warm, dilute (5 %) nitric acid for several hours and then rinse
thoroughly with deionized water.
4b. Clean platinum ware by boiling in dilute (5 %) hydrochloric acid and rinsing thoroughly
with deionized water.
5. Discard the glassware that shows cracks and etching.

52


necessary to prepare fresh working and check standards before each set of measurements or
daily as appropriate.
manufacturer.
will not be interfered with from unexpected elements.
of 2 different wavelengths for the same element.
53
NICKEL, VANADIUM, AND IRON IN CRUDE OILS AND

RESIDUAL FUELS BY INDUCTIVELY COUPLED PLASMA
(ICP) ATOMIC EMISSION SPECTROMETRY: D5708
1. It is extremely important to homogenize the crude or fuel oil in the sample container to
obtain a representative specimen. Otherwise it can lead to erroneous results.
safety practices.
3. Check the temperature and humidity controls of the laboratory containing the ICP-AES


manufacturer.
13. Run the blank and appropriate check standard after every 5th sample. Recalibrate if the net
intensity of the standard changes by more than 5 % relative to the previous check.
54
of two different wavelengths for the same element.
18. Although the use a high-solids Babington type nebulizer is optional in the method, it is
highly recommended that it be used to avoid plugging problems.
than 10 mass % oil.

24. Use of a peristaltic pump is strongly recommended to provide a constant flow of solution.
55
25. Use a base oil free of analytes with viscosity at room temperature close to that of the sample.
PHOSPHORUS IN GF 4 TYPE LUBE OILS BY ICP-AES: D7040

1. Check the temperature control of the ICP and ensure stable environmental conditions. This
can include temperature control of the spray chamber.
2. Employ adequate mixing and sampling procedures. Ultrasonic homogenizers and vortex
mixers are recommended.
3. Use the analytical wavelengths and background correction option specified in the test
method. When there is a choice of analytical wavelengths, choose sensitive lines. Ensure that
the selected lines are not subject to spectral interferences.
4. When spectral interferences cannot be avoided, determine and implement accurate

interference correction factors.
5. When preparing multi-element standards, ensure that the various reagents are mutually
soluble.
6. Before use, check the accuracy of element concentrations of commercially obtained

standards. Either compare with alternative sources or analyze by independent methods.
7. Ensure that all glassware, etc. that contacts samples and standards does not contaminate
them.
8. Select solvents and other reagents that do not contain significant levels of analytes.
Wavelength scanning can indicate contaminated reagents.
9. By experiment, determine the frequency of standards preparation. Then, prepare fresh, as

needed.
10. Periodically, as needed, determine the linearity of the calibration curves. Perform quantitative
analyses with linear curves only.
11. Inspect the torch for cracks. Discard defective torches.
12. Use clean torches that do not have carbon accumulation.
13. After initially igniting the plasma, allow the instrument to warm up a minimum of 30 min.
14. Inspect the peristaltic pump tubing daily, and replace deteriorating tubing. Daily replacement
is recommended.
56
15. Prepare and analyze reagent blanks. When blank values are significant, correct for the blank
or select alternative reagents that give insignificant blank values.
16. To minimize memory effects, allow sufficient solvent rinse time (minimally, 60 s) between
determinations.
17. Report results using the number of significant figures specified in the test method.
18. Dilute the standard oils and sample oils by the same factor. This factor shall be in the range
specified by the test method.
19. Implement internal standardization specified by the test method.
20. When carbon build-up in the torch is problematic, adjust experimental conditions to
eliminate the problem. Such adjustments can include: (1) reducing the sample uptake rate, (2)
increasing the intermediate argon gas flow rate, (3) use a jacketed, chilled spray chamber, (4)
lowering the torch, relative to the RF load coil.
MULTIELELEMENT ANALYSIS OF CRUDE OILS BY

ICP-AES: D7691
1. It is extremely important to homogenize the crude or fuel oil in the sample container to
obtain a representative specimen. Otherwise it can lead to erroneous results.
safety practices.

scan. The net intensity should be zero. In any case, the intensity counts from the blank, or
individual solvent and reagents, be well below the intensity counts associated with the
reporting limit. As a general rule, the blank counts, if not zero, should be ten times lower
than the counts obtained for a standard at the reporting limit.

57
manufacturer.
15. Check for spectral interferences from the elements present in the sample and develop the
necessary correction factors. Follow the manufacturer’s operating guide to develop and apply
the correction factors top compensate for the interferences. Avoid spectral interferences
where possible by judicious choice of wavelength or by comparing the results of two
different wavelengths for the same element.
17. If sulfur is to be determined, do not use commercially available standards that contain
sulfonates. Prepare separate standards with known concentration of sulfur.
18. When analyzing crude oils, use a high-solids Babington type nebulizer to avoid plugging
problems caused by the presence of particulates in the samples. If not corrected, this will
cause low results.
than 10 mass % oil.
58

24. Use of a peristaltic pump is strongly recommended to provide a constant flow of the solution.
SULFUR IN PETROLEUM PRODUCTS BY WAVELENGTH

DISPERSIVE X-RAY FLUORESCENCE SPECTROMETRY:
D2622
1. Provide appropriate training to all personnel authorized to operate the instrument in

accordance with all appropriate government regulations of the user’s country governing the
use of radiation. It is recommended that all personnel operating the instrument should wear
radiation detection badges. If individual radiation badges are not used, then a radiation
detection badge should be mounted on the instrument.
2. Ensure that no unauthorized personnel are able to access and/or operate the X-ray
fluorescence instrument.
3. Employ adequate storage, mixing and sampling procedures. Refrigerate gasolines and similar
volatile materials to retain sample integrity. Expose these materials to ambient conditions
only as long as necessary to obtain a sample for analysis.
3a. Volatile samples may not meet the stated precision of the method because of selective
loss of light materials during analysis.
59
4. Use the peak and background wavelengths recommended in the method. Since spectrometers
from different vendors will have different characteristics, background positions cannot be
specified in the method. The actual background positions used should be determined from a
2-theta scan of the highest and lowest standard to be used in the calibration.
5. For best accuracy it is recommended that the standard and the sample matrix are well
matched. Matrix mismatch can be caused by C/H ratio differences between samples and
standards or by the presence of other heteroatoms in the sample.
6. When the method is applied to petroleum materials with matrices significantly different from
the white oil calibrant specified in this method, caution should be used when interpreting the
results. See section on interferences in the method.
7. When analyzing gasoline blends such as M-85 or M-100 fuels, appropriate correction factors
need to be applied to the results when calibrating with white oil, or calibration standards need
to match the matrix of the samples.
8. It is essential to know the sulfur concentration in the di-n-butyl sulfide standard, not just the
purity, since impurities may also be sulfur containing compounds.
9. Check the film window material (e.g., Mylar) for the presence of analyte. Measure the
magnitude of the contamination and make necessary corrections to apparent
concentrations in samples according to normal analytical practice.
10. Test the film window material with typical samples to be analyzed to check for deterioration.
Samples high in aromatics may dissolve the plastic film.
11. Check the calibration curves when starting a new roll of plastic film.
12. If using reusable sample cells, clean and dry the cells before each use.
12a. Do not reuse the disposable sample cells.
13. Avoid touching the inside of the sample cell, the portion of the window film in the cell, or the
instrument window that is exposed to X-rays. Oil from fingerprints can affect the readings
when analyzing for low levels of sulfur.
14. Wrinkles in the film will affect the intensity of the sulfur X-rays transmitted. Therefore it is
essential that the film be taut and clean to ensure reliable results.
14a. Punch a vent hole in the top of the sample cup when analyzing samples. As the sample
warms, the vapor space above it is also warmed, and the resulting pressure can distort
the film.
14b. Sealed sample cells specifically designed for use with high vapor pressure liquids and
“tube above” instruments are available. They use an insert to remove air from the cup
60
when sealed and, thus, any headspace. These cells can be effectively used for
gasoline samples containing extremely high vapor pressure components, and it is found
that the high vapor pressure components of the sample are contaminating the helium
atmosphere of the optical path. This type of cup is essential if an instrument with the
“tube above” optics is employed. Obviously, it would be undesirable to put a vent hole
in this type of cell.
15. Impurities or thickness variations have been found in polyester films and may vary from lot
to lot. This can affect the measurement of low levels of sulfur. Hence, check the calibration
after starting a new roll or batch of film.
16. Ensure that the sample cell is filled above a minimum depth beyond which additional sample
does not significantly affect the count rate. Generally, fill the sample cell to a minimum of
three-fourths of the cell’s capacity. In any case, always fill to the same level whatever the
size of the cell used. Better yet, for highest accuracy work, fill to the same weight.
17. A sufficient number of counts should be taken to obtain a relative standard deviation of 1 %
or better when practical.
17a. To minimize the effects of heat in the X-ray chamber, use as short a counting time as
possible consistent with good counting statistics.
18. Verify the absence of analyte in all solvents and reagents used. Use the purest available
grades for chemicals to be used for preparing calibration standards.
19. Establish the preparation frequency of the calibration, check, and working standards by
experiments.
20. Prepare or obtain a solid pellet (e.g., fused lithium tetraborate or plastic) containing a
nominal concentration (preferably in the middle or top of the calibration range) of the analyte
for use as instrumental drift monitor. A solid monitor is preferable to a liquid monitor
because of its stability. Glass disks are preferable over fused beads due to the tendency of the
fused beads to pick up moisture. If fused beads are used they should be stored in a desiccator
when not actually being measured. Where appropriate, metal disks are also a good choice.
Plastic pellets are not a good choice as they are not stable with regard to X-ray exposure over
time.
21. Analyze check standards at suitable intervals during analysis of a set of samples, but at least
at the beginning and the end of a series of samples analyzed. Do not report the sample results
if the concentration of the elements in the check standard varies by more than the limits
allowed in the calibration section of the method. Adjust the instrument, re-verify the
accuracy and reanalyze the samples. New portions of the volatile samples will have to be
analyzed.
61
22. If using the automatic sample changer the user should evaluate the effect of evaporation
before using the auto-sampler because samples exposed to ambient conditions for too long
may lose the volatile components.
SULFUR IN GASOLINE BY WAVELENGTH-DISPERSIVE

X-RAY FLUORESCENCE SPECTROMETRY: D6334
1. Fuels with compositions that vary from those specified in the test method may be analyzed
with standards made from base materials that are of similar composition to minimize matrix
effects.
2. Fuels containing oxygenates may be analyzed using standards prepared with similar amounts
of the same oxygenate added to the standard dilution matrix.
3. Methanol fuels (M85 and M100) exhibit interferences at this level of detection (<100 mg/kg).
They can be analyzed using a calibration curve produced by diluting the standards in a
similar matrix of M85 or M100, or by Test method D2622.
magnitude of the contamination and make necessary corrections to apparent concentrations
in samples according to normal analytical practice.
10. Wrinkles in the film will affect the intensity of the sulfur X-rays transmitted. Therefore it Comment [SB1]: Incomplete sentence.
warms, the vapor space above it is also warmed, and the resulting pressure can distort
the film.
62
12. Prepare calibration standards by the careful preparation by mass of a 50:50 mixture (based on
sulfur content) of the certified thiophene and 2-methylthiophene or n-butyl sulfide with 20 to
80 % mixture of toluene-iso-octane or other suitable base material.
13. A sufficient number of counts should be taken to obtain a relative standard deviation of 1%
SULFUR IN PETROLEUM AND PETROLEUM PRODUCTS BY

MONOCHROMATIC WAVELENGTH-DISPERSIVE X-RAY
FLUORESCENCE SPECTROMETRY: D7039
use of radiation.
3. Store gasoline in a leak tight container at 0 to 4°C until ready for analysis. If possible,
maintain at this temperature throughout any transfer and handling processes. Allow the
specimens maintained at 0 to 4°C to reach room temperatures before testing and expose these
materials to ambient conditions only as long as necessary to obtain a sample for analysis.
Analyze test specimens as soon as possible after sub-sampling from bulk container. Do not
allow bulk container to remain uncovered any longer than is needed to obtain desired sub-
sample.
4. Volatile samples may not meet the stated precision of the method because of selective loss of
light materials during analysis. Use the utmost care in sampling and handling gasoline to
prevent evaporation of light ends which could change the concentration of sulfur in the
samples.
5. For fuel samples containing large quantities of oxygenates (biodiesel, biodiesel blends,
gasoline-ethanol blends) can have a high oxygen content leading to significant absorption of
sulfur K alpha radiation and low sulfur results. In such cases matrix of calibration standards
should be either matched to the sample matrices, or the matrix correction described in the test
method be applied to the results.
6. When the elemental composition of the samples differ significantly from the calibration
standards used to prepare the calibration curve, the cautions and recommendations given in
the test method should be carefully observed.
63
7. Differences between the elemental composition of the test samples and the calibration
standards can result in biased sulfur results. The interfering elements of concern are carbon,
hydrogen, and oxygen.
8. Other samples having interferences may be analyzed by applying correction factors to the
results or by using calibration standards that are matrix matched to the test sample.
9. To minimize any bias in the results, use calibration standards prepared from sulfur-free base
materials of the same or similar elemental composition as the test samples. When diluting the
samples, use a diluent with an elemental composition the same or similar to the base material
used for preparing the calibration standards.
10. A base material for gasoline can be approximately simulated by mixing iso-octane and
toluene in a ratio that approximates the expected aromatic content of the samples to be
analyzed.
11. Any film resistant to chemical attack by the sample, free of sulfur, and X-ray transparent can
be used, e.g., polyester, polypropylene, polycarbonate, and polyimide. However, samples of
high aromatic content can dissolve polyester and polycarbonate films.
12. Because impurities and thickness variations can occur in commercially available transparent
films and vary from lot to lot, use calibration-check samples to verify calibration integrity
after starting each new batch of film.
13. It is essential to know the concentration of sulfur in the di-n-butyl sulfide, not just the purity,
since impurities can also be sulfur-containing compounds.
14. Calibration standards may be used as drift monitor samples. Because it is desirable to discard
test specimens after each determination, a lower cost material is suggested for daily use. Any
stable material can be used for daily monitoring of drift.
15. Ensure that the MWDXRF analyzer has been installed and put into operation according to
manufacturer’s instructions. Allow sufficient time for instrument electronics to stabilize.
Perform any instrument checkout procedures required. When possible, the instrument should
be run continuously to maintain optimum stability.
16. Use the count time recommended by the instrument manufacturer for the lowest sulfur
concentration expected. The typical time each measurement is two to three minutes.
17. Carefully transfer a sufficient portion of the liquid to fill an open-ended sample cell above a
minimum depth of 5 mm, beyond which additional liquid does not affect the count rate.
Filling the sample cell to three-fourths of the cell’s depth is generally adequate.
64
18. Fit an unused piece of X-ray transparent film over the sample cell opening and attach
securely. Use the same batch of film for the analysis of test samples and the calibration
standards used for constructing the calibration curve.
19. Avoid touching the inside of the sample cell, any portion of the film exposed to the liquid or
the X-ray beam, and also avoid touching the instrument window. It is highly recommended
that clean, disposable rubber or plastic gloves be used when preparing test specimen. Ensure
that the film is taut, wrinkle-free, and not leaking.
20. Provide a small vent to prevent bowing of the window cell by the accumulating vapor.
21. Perform the specimen analysis promptly after preparing the specimen. Do not let the
specimen remain in the sample ell any longer than necessary before collecting the data.
22. Obtain or prepare a set of calibration standards bracketing the expected concentration range
in the samples by careful mass dilution of di-n-butyl sulfide with a suitable base material.
Two suitable base materials are mineral oil and ethanol. All standards used in the analyses
must be from a reliable and consistent source.
23. Immediately after analyzing the calibration standards, determine the sulfur concentrations of
one or more calibration-check samples. The determined value shall be in the range defined
by the certified concentration ± the repeatability of this test method. If this criterion is not
met, the calibration process and the calibration standards are suspect, corrective measures
must be taken, and the calibration rerun. The degree of matrix mismatch between the
calibration check samples and should be considered when evaluating a calibration.
24. Verification of system control through the use of quality control samples and control charting
is highly recommended.
25. Report the sulfur concentration of the test sample rounded to the nearest 0.1 mg/kg for
concentrations of <100 mg/kg, and rounded to the nearest 1 mg/kg for concentrations greater
than or equal 100 mg/kg.
SULFUR IN PETROLEUM AND PETROLEUM PRODUCTS BY

ENERGY-DISPERSIVE X-RAY FLUORESCENCE
SPECTROMETRY: D4294
use of radiation.
65
3. Volatile samples may not meet the stated precision of the method because of selective loss of
light materials during analysis.
4. The standard and the sample matrix must be well matched. Matrix mismatch can be caused
by C/H ratio differences between samples and standards or by the presence of other
heteroatoms in the sample.
5. When the method is applied to petroleum materials with matrices significantly different from
the white oil calibrant specified in this method, caution should be used when interpreting the
results. See section on calibration in the method.
6. When analyzing gasoline blends such as M-85 or M-100 fuels, appropriate correction factors
need to be applied to the results when calibrating with white oil, or calibration standards need
to match the matrix of the samples.
7. There could be spectral interferences as well as matrix interferences which are generally
taken care of by the software offered by the instrument manufacturers. However, it is
recommended that these interferences be checked from time to time, and that the software
corrections offered by the manufacturers not be accepted at face value. Corrections should be
verified for new formulations.
8. If the samples contain suspended water it must be removed from the sample before the
analysis, or it must be thoroughly homogenized and immediately tested. However, it is
possible that water may separate on standing during long counts.
10. Store all standards and quality control materials in glass bottles, either dark or wrapped in
opaque material, closed with glass stoppers, inert plastic lined screw caps, or other equally
inert, impermeable closures, in a cool dark place until required. Discard the material as soon
as any sediment or change of concentration is observed.

66
16a. Punch a vent hole in the top of the sample cup when analyzing samples. Sealed sample
cells are available for use with samples with high vapor pressure.
three-fourths of the cell’s capacity. The key is to always fill to the same level whatever the
size of the cell used. Better yet, for highest accuracy work, fill to the same weight.
experiments.
at the beginning and the end of a series of samples analyzed. Do not report the sample results
if the concentration of the elements in the check standard varies by more than 3 % of the
certified concentration. Adjust the instrument, re-verify the accuracy and reanalyze the
samples. New portions of the volatile samples will have to be analyzed.
23. It is strongly recommended that whenever possible the calibration is matrix specific, that is, a
diesel calibration be based on diesel standards. This is especially true for determination of
sulfur at low levels.
24. If using an automatic sample changer the user should evaluate the effect of evaporation
67
ELEMENTAL ANALYSIS OF LUBRICANT AND ADDITIVE

COMPONENTS – BARIUM, CALCIUM, PHOSPHORUS,
SULFUR, AND ZINC BY WAVELENGTH DISPERSIVE X-RAY
FLUORESCENCE SPECTROSCOPY: D4927

use of radiation. It is recommended that all personnel operating the instrument should wear
radiation detection badges. If individual radiation badges are not used, then a radiation
detection badge should be mounted on the instrument.
3. Employ adequate storage, mixing and sampling procedures. Expose these materials to
ambient conditions only as long as necessary to obtain a sample for analysis.
4. Use the analytical parameters suggested in Tables 2 and 4 of the method.
5. The additive elements found in lubricating oils will affect the measured intensities from the
elements of interest to a varying degree. These effects can range from 0.03 mass % due to the
heavier elements to 1 mass % for the lighter elements. These interferences can be
compensated by mathematical correction or by use of internal standards. If the element is
present at significant concentrations and an inter-element correction for that element is not
employed, the results can be low due to absorption or high due to enhancement.
in samples. Use the same film batch throughout the entire analysis.
68
11. Wrinkles in the film will affect the intensity of the sulfur and phosphorus X-rays transmitted.
Therefore it is essential that the film be taut and clean to ensure reliable results.
warms up, the vapor space above it is also warmed, and the resulting pressure can
distort the film.
11b. Sealed sample cells are available for use with high vapor pressure samples and
instruments with “above tube” configurations. They may be advantageous to use in
such cases.
to lot. This can affect the measurement of low levels of sulfur and phosphorus. Hence, check
the calibration after starting a new roll or batch of film.
does not significantly affect the count rate. Generally, fill the sample cell at least half full of
the cell’s capacity. In any case, always fill to the same level whatever the size of the cell
used. Better yet, for highest accuracy, fill to the same weight.
or less when practical.
experiments.
17. Prepare or obtain a solid pellet (e.g., fused lithium tetraborate or plastic) containing a
nominal concentration (preferably in the middle or top of the calibration range) of the analyte
for use as instrumental drift monitor. A solid monitor is preferable to a liquid monitor
because of its stability. Glass disks are preferable over fused beads due to the tendency of the
fused beads to pick up moisture. If fused beads are used, they should be stored in a desiccator
when not actually being measured. Plastic pellets are not a good choice as they are not stable
with regard to X-ray exposure over time.
LEAD IN GASOLINE BY XRF: D5059

1. Provide appropriate training to all personnel authorized to operate the XRF instrument in
accordance with all government regulations governing radiation. All personnel operating the
instrument must wear finger and body radiation detection badges.
69
2. Employ adequate storage, mixing, and sampling procedures. Refrigerate gasoline samples
and similar volatile materials to retain sample integrity. Expose these materials to ambient
conditions only as long as necessary to obtain a specimen for analysis.
3. Use the analytical and background wavelengths specified in the method because they have
been established by experiment to be the optimum wavelengths.
4. Check the film window material (e.g., Mylar) for the presence of analytes. Measure the
magnitude of contamination and make the necessary corrections to apparent concentrations
5. Check the film window material with typical samples to be analyzed to check for
deterioration. Samples high in aromatics may dissolve the plastic film.
6. Check calibration curves when starting with a new roll of plastic film.
grades for chemicals to be used for preparing standards. If the analyte is found in significant
concentrations either discard the chemicals or make the necessary corrections to the final
concentration of analyte in the samples.
8. Use NIST lead in gasoline Standard Reference Materials to assist in developing the initial
calibration curves and for subsequent checking of secondary standards.
experiment.
10. Avoid contaminating the sample cups, particularly from touching the inside of the cups with
bare fingers.
11. When covering the specimen in the sample cups with plastic film, be sure that no wrinkles or
bulges exist. Punch a vent hole in the top of the sample cup when analyzing volatile samples
such as gasoline.
at the beginning and the end. Do not report sample results if the concentrations of analyte in
the check standard vary by more than 5 % of the certified concentration of the standard.
Adjust the instrument, re-verify accuracy, and reanalyze the samples. Note that new portions
of volatile samples will have to be analyzed.
13. If analyzing RFG samples, prepare the above standards containing representative
concentrations of oxygenates. Standards for M85/M100 fuels should be prepared using
reagent grade methanol. Verify the absence of analyte in the methanol prior to use.
14. Use lead naphthenate to prepare standards, not lead tetraalkyls, which are highly toxic and
cannot be safely used in a normal laboratory environment.
70
15. Avoid using an automatic sample changer because samples are exposed too long to ambient
temperature before analysis allowing volatile components to escape.
16. Use as short a counting time as possible, but also consistent with good counting statistics, to
minimize the effects of heat in the X-ray chamber.
TRACE METALS IN PETROLEUM COKE BY WD-XRF: D6376

1. Review all potential spectral interferences for the elements in the scope of this method.
Follow the manufacturer’s operating guide to develop and apply alphas to compensate for
these interferences.
2. Compensate for the inter-element effects by using alphas as part of the regression procedure
provided with the spectrometer software.
3. Changes in the sulfur concentration in the sample affects analyte X-ray intensities. Therefore,
determine the magnitude of the sulfur effect on each metallic element and apply in
appropriate correction.
4. Results are particle dependent, and erroneous data may be collected if analytical sample
contains particles varying significantly in size from those in the reference samples.
Measurements may be necessary to ensure the equivalence of analytical and reference
samples. The most difficult problems occur when there are coarse petroleum coke samples
and finely ground reference samples. In this case, it is best to grind the analytical samples,
achieving a size distribution similar to the reference sample.
5. It is essential that the same sample preparation procedure (including sample mass, binder
mass and ratio, grinding, and so forth) be followed precisely for all analytical and reference
samples. Even a small change in procedure requires making all new reference samples match
the changed procedure. All reference samples and analytical samples used with them shall be
prepared in exactly the same manner. All weighings are to be made to the nearest 0.01 g.
6. It is recommended that reference samples used for calibration be verified by Test Method
D1552 for sulfur, by Test method D5600 or D5056 for metals, or by using other techniques
considered standards in the industry, such as spectrophotometry.
METALS IN LUBE OILS AND ADDITIVES BY WDXRF: D6443
1. In accordance with the regulations governing the use of ionizing radiation, provide training to
all personnel authorized to operate the X-ray instrument. Provide finger and body radiation
detection badges for operators. Do not disable any of the X-ray instrument’s safety features.
71
2. Use appropriate sample storage and mixing procedures. When analyzing additives and
additive packages by dilution, ensure satisfactory mixing of the diluted sample.
3. Use the peak and background wavelengths (angles) specified in the test method because they
have been found satisfactory by experimentation.
4. Determine if the sample cell film contains a significant concentration of any analyte
(typically, indicated by the D value in the concentration-intensity model, Eq. 10. Avoid using
film that contains a significant concentration of the analyte.
5. Determine the integrity of the sample cell film when it is in contact with the sample. Some
sample types can dissolve certain types of films. Analyze samples as soon as possible after
filling the sample cells.
6. Avoid contamination of the sample cells by touching the inside of the cell or the film.
7. Avoid using sample cells when the attached film wrinkles or bulges.
8. Punch a vent hole in the top of a filled sample cell.
9. When a new container or batch of sample cell film is used, check all calibration curves.
10. Confirm the absence of analytes in diluents and stabilizers. For preparation of calibration
standards, use reagent grade chemicals with certified concentrations of the relevant analytes.
11. Obtain sufficient quantities of quality control samples for each type of samples analyzed
(e.g., an automotive lube oil, an additive package, etc.). Ensure that these quality control
samples will remain uniform for a reasonable period (typically, one year). If such samples are
not available, synthesize the QC samples from oil-soluble standards.
12. For each QC sample, define a frequency of analysis and control limits. Implement this QC
protocol.
13. Establish a list of corrective actions that can be implemented when the results from a QC
analysis are outside control limits.
14. Prepare or obtain solid pellets (e.g., glass, fused lithium tetraborate, plastic, etc.) containing
the various analytes. These pellets can serve as monitors to determine and correct drift
caused by performance changes in the X-ray instrument.
15. Analyze U.S.P. white (mineral) oil, which can serve as a blank. Results obtained on a blank
can be subtracted from sample results to correct for film impurities and drift in the calibration
intercept.
SULFUR IN GASOLINE BY ENERGY DISPERSIVE X-RAY

FLUORESCENCE SPECTROMETRY: D6445
72

use of radiation.
4. Fuels with compositions that vary from those specified in the standard may be analyzed with
standards made from base materials that are of similar composition to minimize matrix
effects.
5. Fuels containing oxygenates may be analyzed using standards prepared with similar amounts
of the same oxygenate added to the standard dilution matrix.
6. Methanol fuels (M85 and M100) exhibit interferences at this level of detection (<100 mg/kg).
They can be analyzed using a calibration curve produced by diluting the standards in a
similar matrix of M85 or M100 or by Test Method D2622.
7. The standard and the sample matrix must be well matched. Matrix mismatch can be caused
by C/H ratio differences between samples and standards or by the presence of other
heteroatoms in the sample.
8. Do not touch inside of the XRF sample cup, the portion of the window film in the cup, or the
instrument window that is exposed to X-rays. Oil from fingerprints can affect the reading
when analyzing for low levels of sulfur. Wrinkles in the film will affect the number of sulfur
X-rays transmitted. Therefore, the importance of film’s tautness and cleanliness cannot be
overstressed. Disposable sample cups are not to be reused. Renewal of the windows of the
sample cup is essential for the measurement of each sample.
9. Recalibrate the analyzer when you change the type or thickness of the window film.
10. Polyester films often contain impurities that may affect the measurement of low levels of
sulfur, and may vary from lot to lot. Therefore, if using a polyester film, check the calibration
with the start of each new roll.
73
13. X-ray films may vary in thickness from batch to batch. Check the calibration when starting a
new roll of any film.
15. Samples of high aromatic content may dissolve polyester and polycarbonate films. In these
cases, other materials besides these films may be used for X-ray windows, provided that they
do not contain any elemental impurities that can adversely affect the results obtained by this
test method.
16. Take a sufficient number of counts to satisfy at least 1 % expected coefficient of variation
when practical.
17. There could be spectral interferences as well as matrix interferences which are generally
taken care of by the software offered by the instrument manufacturers. However, it is
recommended that these interferences be checked from time to time, and that the software
corrections offered by the manufacturers not be accepted at face value. Corrections should be
verified for new formulations.
18. If the samples contain suspended water it should be removed from the sample before the
analysis, or it should be thoroughly homogenized and immediately tested. However, it may
separate if long counting times are used.
19. It is essential to know the sulfur concentration in the di-n-butyl sulfide, thiophene, and 2-
methylthiophene standards, not just the purity, since impurities may also be sulfur containing
compounds.
20. Store all standards and quality control materials in glass bottles, either dark or wrapped in
opaque material, closed with glass stoppers, inert plastic lined screw caps, or other equally
inert, impermeable closures, in a cool dark place until required. Discard the material as soon
as any sediment or change of concentration is observed.
21. If using reusable sample cells, clean and dry the cells before each use. Do not reuse the
disposable sample cells.
warms, the space above it is also warmed, and the resulting pressure can distort the
film.
74
three-fourths of the cell’s capacity. In any case, always fill to the same level whatever the
size of the cell used. Better yet, for highest accuracy, fill to the same weight.
24. The measured sulfur concentration may vary with the time that the sample/standard contacts
the film covering the sample cell. Possible variations can be reduced by consistently
minimizing the length of time the film comes into contact with the sample/standards.
experiments.
at the beginning and the end of a series of samples analyzed.
27. It is strongly recommended that whenever possible the calibration is matrix specific, that is, a
diesel calibration be based on diesel standards. This is especially true for determination of
sulfur at low levels.
28. If using an automatic sample changer the user should evaluate the effect of evaporation
METALS IN LUBE OILS BY ED-XRF: D6481

1. Avoid using sample cell films other than the ones recommended. Polyester films may contain
impurities of silicon, phosphorus, and calcium.
2. If the instrument uses a secondary safety window, ensure that it is clean before measuring
each sample. If in doubt, then change it.
3. Avoid contamination of the sample cell window. Do not touch it with fingers.
4. Ensure that the sample cell windows are flat and free of wrinkles.
5. When a new container or a batch of sample film is used, check the method with the QC
check sample.
6. Establish a list of corrective actions that can be taken when results from a QC test are outside
control limits. The instrument supplier may be able to advise on this.
7. Analyze the diluent solvent as an additional QC sample from time to time to confirm that
there is no contamination in the instrument.
ADDITIVE ELEMENTS IN LUBRICATING

OILS BY ED-XRF: D7751
75
1. In general the X-radiation emitted by the elements of interest can be absorbed by itself (self-
absorption) or by the other elements present in the sample matrix. Also, the X-radiation
emitted from one element can further excite (enhance) another element. These inter-element
effects are significant at concentrations varying from 0.03 mass %, due to the higher atomic
number elements (e.g., molybdenum) to 1 mass % for the lower atomic number elements
(e.g., sulfur). If an element is present at significant concentrations and an inter-element
correction for that element is not employed, the results can be low due to absorption or high
due to enhancement.
2. Absorption and enhancement effects will be corrected by corrections from the fundamental
parameters approach or by other matrix correction models.
3. There can be spectral overlap of one element onto another, and the instrument must include
correction procedures for any such overlap.
4. Verification of system control through the use of QC samples and control charting is highly
recommended.
5. Impurities or thickness variations, which may affect the determination of low levels of
analytes, have been found in polyester films and may vary from lot to lot. Therefore, the
method shall be verified after starting each new roll or batch of film. When opening a new
roll of film, it may be recommended to discard the first meter as some films are packaged in
plastic bags that contain sulfur.
6. When connecting a new helium cylinder, always run a blank measurement to ensure the
helium gas line is purged of air. When using QC samples, check the performance by running
the QC sample(s).
7. It is recommended that each sample is prepared and analyzed immediately. Also, it is

recommended that care be taken not to leave the test sample in the instrument after the
measurement process has finished.
XRF Aids to the Analyst

Area Recommended Suggestion
Safety In accordance with regulations governing the use of ionizing
radiation, provide training to all personnel authorized to operate the
X-ray instrument. Provide finger and body radiation detection badges
for operators. Do not disable any of X-ray instrument’s safety
features.
Exposure to excessive quantities of high energy radiation such as
those produced by X-ray spectrometers is injurious to health. The
operator needs to take appropriate actions to avoid exposing any part
of their body to primary, secondary, or scattered radiation that might
be present. The X-ray spectrometer should be operated in accordance
76
with the regulations governing the use of ionizing radiation.

Sampling Employ adequate storage, mixing, and sampling procedures.
Refrigerate gasolines or other similar volatile materials to retain
sample integrity in storage, but allow them to return to room
temperature before testing. Expose these materials to ambient
conditions only as long as necessary to obtain a sample for analysis.
Samples should be analyzed immediately after pouring into a sample
cup and allowing for the escape of the air bubbles caused by mixing.
In case of samples containing suspended water, it should be removed
before testing or that the sample be thoroughly homogenized and
immediately tested. The interference is greatest if the water creates a
layer over the transparent film as it will attenuate the X-ray intensity
for sulfur. One such method to accomplish the removal of water is to
centrifuge the sample first under ambient sealed conditions, taking
care not to compromise the sample integrity.
Sample Cells When reusable sample cells are used, clean and dry cells before each
use. Disposable sample cells shall not be reused. Avoid touching the
inside of the sample cell, the portion of the window film in the cell, or
the instrument window that is exposed to X-rays. Oil from the
fingerprints can affect the reading when analyzing for low levels of
analytes.
After the sample cell is filled, create a small vent hole at the top
except when the cell is of sealed type.
Volatile Samples Samples such as high vapor pressure gasolines or light hydrocarbons
may not meet the stated precision because of selective loss of light
materials during the analysis.
Sample Matrix Fuels containing large amounts of FAME, ethanol, or methanol have
a high oxygen content leading to significant absorption of sulfur K
alpha radiation and low sulfur results. These samples should be
analyzed with either the correction factors are applied to the results
when calibrating with white oil, or the calibration standards should be
prepared to match the sample matrix.
Oxygenated Oxygenated fuels with ethanol or methanol contents exceeding limits
Fuels given in the test method can be dealt with using the test method but
the precision statement given in the test method may not apply.
For samples with high oxygen contents ( > 3 mass %) sample dilution
should be used or matrix matching must be performed to assure
accurate sulfur results.
Scope Samples containing more than 4.6 mass % sulfur should be diluted to
bring the sulfur concentration of the diluted material within the scope
of the test method. Such diluted samples can have higher errors than
indicated in the precision section of the test method.
Test Method D4927 is better suited for determining sulfur in lube oils
and additives because it implements inter-element correction factors.
Test Method D2622 is not suitable for such work because it does not
encompass the measurement of additional elements present making
77
correction impossible.
Standards The standard and sample matrices should be well matched, or the
matrix differences should be accounted for. Matrix mismatch can be
caused by C/H ratio differences between samples and standards or by
the presence of other interfering heteroatoms or species.
Petroleum materials that vary in composition from white oils can be
analyzed with standards made from base materials that are of same or
similar composition.
Storage of Store all standards in either in dark or wrapped in opaque material
Standards glass bottles, with screw caps with a chemically resistant lining or
with glass stoppers, in a cool, dark place until required. As soon as
any sediment or change of concentration is observed, discard the
standard.
Calibration The concentration of unknown samples must lie within the calibration
range that is used. Take into account any analyte in the base material
when calculating the concentration of standard.
Calibration Commercially available standards can be used provided their analyte
Standards concentrations are accurately known and they approximate the
nominal concentrations listed in the test methods.
When using internal standards such as bismuth 2-ethylhexoate in lead
determination, some stability difficulties have been reported.
Standards containing 100 mg/kg total sulfur or less must be analyzed
in duplicate. Average values of these measurements can be used in
the calibration. All samples in this sulfur range must also be analyzed
in duplicate. Each determination must be made on a new portion of
the sample material and the difference between the duplicate analyses
should be equal to or less than the repeatability of the test method. If
the difference is larger, investigate sample preparation to identify any
possible sources of sample contamination, and repeat the analysis.
The reason for duplicate measurements is to identify problems
associated with sample contamination, leading to improved results
precision at the lower analyte levels.
Calibration These should not be the same ones that were used for preparing the
Check Standards calibration curve. The check samples are used to determine the
precision and accuracy of the initial calibration.
The difference between measured values of two check standards shall
be within the repeatability of the test method. When this is not the
case, the stability of the instrument and the repeatability of the sample
preparation are suspect and corrective measures should be taken.
Sulfur Standards It is essential to know the sulfur concentrations in the bi-n-butyl
sulfide, not only the purity, since impurities may also be sulfur
containing compounds. The sulfur content may be determined via
mass dilution in sulfur-free white oil followed by a direct comparison
analysis against NIST (or other primary standard body) reference
materials.
78
Mineral Oil When used for preparing sulfur standards should contain less than 2
mg/kg sulfur. When the sulfur content of the solvent or reagent is not
certified, verify the absence of sulfur. Use the purest grade for
preparing calibration standards. It is also important to measure the
C/H ratio.
Drift Correction These monitors should be made from stable materials non-degradable
Monitor to repeated exposure to X-rays.
The monitor’s counting rate, in combination with count time, shall be
sufficient to give a relative counting error of less than 1 %. .
Sample Counts A sufficient number of counts be taken to satisfy an expected
coefficient of variation (i.e., % RSD) of 1 % or less when practical.
Film The film used to cover the sample cells must be free of analyte, resist
attack by the sample and/or solvent, and sufficiently X-ray
transparent. Samples of high aromatic content can dissolve
polypropylene and polycarbonate films. Wrinkles in the film covering
the sample cells will affect the intensity of the X-rays transmitted,
Therefore, it is essential that the film be taut and clean to ensure
reliable results. The analyzer may need to recalibration if the type or
thickness of the window film is changed.
Impurities or thickness variations, which may affect the measurement
of low levels of sulfur, have been found in polyester films and may
vary from lot to lot. Therefore, the calibration should be checked after
starting each new lot of film.
The measured sulfur concentration may vary with the time that the
sample/standard contacts the film covering the sample cell. By
consistently minimizing the length of time the film comes into
contact with the sample or standards, possible variations can be
reduced.
Where a laboratory uses more than one XRF spectrometer or analyzes
different types of samples, a variety of cell window materials may be
used. Always ensure that the correct film is clearly distinguished.
Discard any film that has been exposed to the atmosphere, e.g.,
hanging outside of the film roll dispensing box. Also, when opening a
new roll of film, discard the first meter, since some films are
packaged in plastic bags that contain sulfur.
Interferences When the sample is known or believed to contain concentrations of
interfering substances higher than the levels listed in the test method,
dilute the sample by mass with base material to concentrations to
below those listed.
The additive elements found in lube oils will affect the measured
intensities from the elements of interest to a varying degree. These
effects are significant from at concentrations varying from 0.03 mass
% due to the heavier elements to 1 mass % for the lighter elements.
This can be mathematically corrected or compensated using internal
standards. If an element is present at significant concentrations and an
79
interelement correction for that element is not employed, the results

can be low due to absorption or high due to enhancement.
Counting Gas For instruments equipped with flow proportional counters, the purity
of the counting gas should be in agreement with the specifications
provided by the instrument manufacturer.
Regular checks should be carried out to ensure that purging gas
performance is within the instrument manufacturer’s specification.
When connecting to a new inert gas cylinder, always run a blank
measurement to ensure the inert gas line is purged of air.
Validation Once a standard or a sample has been measured, the operator should
check for obvious signs of damage to the sample such as leaking
sample cells, crinkled sample cell window and inspection of any
secondary film.
If a result is considered outside normal thresholds, a repeat of the
analysis should be carried out to confirm anomalous results.
Quality Control Verification of system control through the use of QC samples and
control charting is highly recommended.
QC samples should be available in large enough quantities, well-
characterized, and stable over a long period of time.
In addition to running a QC sample, it is strongly recommended that
the calibration blank (e.g., diluent oil) be analyzed on a daily basis.
When analyzing more than a single unknown sample, measure a QC
sample at the end of each batch of unknown samples, but no less than
every ten unknown samples, to verify that the method is in control. In
all situations where The QC sample results vary by more than the
repeatability of the test method, the analysis must be discontinued,
and corrective action taken to find the source of the error.
Reporting Report the results to three significant figures for concentrations
greater than 0.1 mass %. Below that level, report results in mg/kg to
three significant figures, and to two significant figures below 10
mg/kg.
For samples containing 100 mg/kg of total sulfur or less, average the
duplicate determinations and report that value.
See ASTM Test Methods D2622, D4294, D4927, D5059, D6334, D6443, D6445, D6481,
D7039, D7212, D7220, and in particular D7343 for further explanation.
MICROCARBON RESIDUE: D4530

1. An exhaust system should be provided to remove small amounts of smoke produced during
carbon residue testing. Any suction line used to draw the smoke away should not be
connected directly to the MCRF chimney. Allow a small space between the chimney and the
suction line. This prevents a negative pressure from being created within the apparatus.
80
2. The sample vials should be handled only with gloved hands or forceps.
3. The large four-dram vials should be used only for light oils and the samples that are expected
to yield residue less than 0.10 m/m %.
4. The final residue should be less than about 50 mg and preferably around 25 mg. If too much
sample is taken, the material may boil over during heating, especially with high residue oils.
Use the equation and the table given in the test method as a guide for recommended sample
mass to be taken.
5. If there is spattering or foaming of samples during the initial heating stage, this may be due to
the presence of water in the sample. A smaller sample size can be used, or the water can be
removed by gentle heating in vacuum, followed by a nitrogen sweep.
TOTAL NITROGEN IN LUBRICATING OILS AND FUELS
There are several test methods for nitrogen determination in petroleum products using multiple
analytical techniques.
ASTM Test Method Technique Page

D3228 Kjeldahl digestion and titration 76
D4629 Combustion & Chemiluminescent Detection 77
D5291 Combustion & Instrumental Detection 77
D5762 Combustion & Chemiluminescent Detection 77
D3228: NITROGEN ANALYSIS BY

MODIFIED KJELDAHL METHOD
1. The nitrogen in the sample must be in the form of an amine or an amide. The method is not
applicable to nitrogen present as nitrate or in heterocyclic compounds containing N-O or N-N
linkage. In such cases lower results will be obtained compared to true total nitrogen
concentration.
2. Normality of the sulfuric acid (0.05 M) used must be periodically checked.
3. If during titration, a reading of < 1 mL of 0.05 M sulfuric acid is obtained, the analysis
should be repeated with a 0.005 M sulfuric acid titrant.
4. The digestion flask must be connected to the distillation apparatus immediately after the
alkali solution has been added and layered, but before swirling to mix the acid and alkali.
When any mixing is permitted to occur before the digestion flask is connected, the heat
generated can be sufficient to release some of the ammonia which may be lost. This will
result in low recovery of ammonia, and thus low values for the nitrogen content of the
sample.
81
5. During distillation, heat must be applied promptly to the digestion flask, to prevent sucking
of the boric acid solution into the condenser as the digestion solution cools.
6. The initial distillation rate must not be too rapid because most of the ammonia is distilled
during the first few minutes, and if too large an amount is present, it may not be all absorbed
instantly in the boric acid solution.
7. A blank should be run with every set of samples, identical in every way with the regular
determinations, except 1.0 g of sucrose is added instead of the sample. The initial volume of
20 mL sulfuric acid is all that is used for the digestion of the sucrose.
D4629 & D5762: NITROGEN ANALYSIS BY OXIDATIVE COMBUSTION

AND CHEMILUMINESCENT DETECTION
1. A range of samples may be analyzed by varying the sample inlet system:
1a. Syringe inlet for materials having boiling points below 350°F such as gasoline. It may
also be used for aqueous samples if the instrument is calibrated with aqueous standards.
1b. Boat inlet for samples having boiling points between 350 and 900°F, such as distillates and
diesel fuels.
1c. Solid sample inlet coupled to a programmable furnace for higher boiling and viscous liquids
such as whole crude oil, additives, and lubricating oils.
2. Furnace Temperature: 1050°C ± 25°C required for nitrogen. The use of quartz chips in the combustion
zone of the pyrotube is required.
3. Needle Tip Position during Injection: The needle tip should be presented fully in to hottest part of the inlet
area of the furnace. Assembly of apparatus to manufacturer's specification and full insertion of the
needle will assure this.
4. Injection Peak/Needle Blank: Avoid integration of any baseline upset caused by the needle
penetration of the septum. After the sample specimen has been measured into the syringe, retract the plunger to
form an air gap up to approximately the 10% scale mark of the syringe barrel. Insert the syringe needle
into the injection inlet and allow the needle/septum blank to dissipate. Reset the instrument
baseline or enable integration, if required, prior to the injection of the syringe contents.
5. Residence Time of needle in Furnace: Residence time of the needle in the furnace must be
consistent following the injection of the sample. For direct injections it is recommended that the needle remain
in the furnace until the instrument returns to baseline and the analysis of the injected material is
complete.
82
6. Boat Path: The boat should be presented fully into the inlet area of the furnace. Assembly of the
apparatus to the manufacturer's specification assures this.
7. Boat Entry Rate and Resident Time of Sample in Furnace: Insert the boat into the furnace using a drive rate
of 140-160 mm/minute (Model 735 setting of 700 - 750). Additional slowing of boat speed or briefly pausing the
boat in the furnace may be necessary to assure complete sample combustion. The boat should emerge from the
99 furnace soon after nitrogen detection is complete. Boat in furnace residence times can vary
depending on sample volatility and levels of Nitrogen measured. Typical boat in furnace residence times
8. Injection Rate and Frequency: Discharge contents of the syringe into the boat at a slow rate
(approximately on pL/second) being careful to discharge the last drop. Use of quartz wool in the sample
boat to aid quantitative delivery is advised.
9. Boat Temperature at Time of Sample Introduction: Sample volatility must be addressed; be sure
boat temperature has returned to ambient or sub-ambient temperatures prior to introduction of sample into
boat. Let boat rest at least 2.5-3 minutes in water jacket or cooling area between injections, some nitrogen
may be measured as the sample evaporates as the boat approaches the furnace. Sub-ambient temperature
can reduce this evaporation.
10. Boat Blank/Baseline Stability: Prior to analysis, especially when analyzing low levels, advance empty
boat into furnace to assure that no contamination is present in the boat or on the inside areas of the pyrorube
near the injection area. Heat empty boat in furnace to assure that boat is clean, then rapidly move boat out
to injection area.
Note: If the hot boat being returned to injection area caused nitrogen to be detected,
repeat the boat in the out cycle, until no nitrogen is measured. For a given gain factor,
photomultiplier tube voltage cab be adjusted to insure maximum sensitivity while maintaining a stable,
noise-free baseline.
11. Injection Size: As a general rule larger sample sizes are required for measurement of lower levels of
nitrogen. While determining the best sample size, frequently check for evidence of incomplete
combustion (sooting) that may be present in the sample path. Control sooting by slowing the injection rate of
the sample from the syringe, and increasing the pyro-oxygen or inlet oxygen supply. Suggested sample
sizes are as follows:
Trace to 5 ppm 10-20 µL

5 ppm to 100 ppm 5-10 µL
100 ppm to percent 5 µL
12. Using sample injection amount by weight is a more accurate method than using volume
measure, provided a balance with a precision of ±0.01 mg is used.
13. Injection Rate and Frequency: Discharge contents of the syringe into the furnace at a slow
rate, approximately one ^iL / second (Model 735 Sample Drive rate of 700 - 750). Frequency
of injection can vary depending upon sample and syringe handling techniques, rate of
83
injection and needle in furnace residence time. Typical injection frequency allows at least 2.5
minutes between injections.
14. Flow Path, Leak Check and Back Pressure: The sample flow path must be leak free when
pressure tested per the manufacturer's recommended procedure (2-3 PI). Flow path back
15. Gas Flow Settings: Gas supplies to various pints in the sample path must be consistently controlled to
allow for smooth, complete combustion of the sample.
Typical Gas Flows:

Inlet Carrier Flowmeter 3.4-3.6 130-160 mL/min
Settings*
Inlet Oxygen Flowmeter 0.4-0.6 10-20 mL/min
Setting
Furnace Oxygen Setting 3.8-4.1 450-500 mL/min
Ozone Generator Flowmeter 1.5-1.7 35-45 mL/min
Setting**
* Helium or argon may be used as a carrier gas.
**Flow to ozone generator.
16. Membrane Dryer Purge: Water produced during the combustion of the sample is removed
by the membrane dryer. This water must then be purged from the membrane dryer. For an apparatus that
utilizes a desiccant scrubber to provide the membrane dryer purge gas, replace the drying agent when
color change (blue to pink) indicates. When a auxiliary gas flow is used, set membrane dryer purge flow at
200-250 mL/minute.
17. Sample Homogeneity/Calibration Response: Prior to analysis, mix samples and calibration materials
well. Minimum response should be no less than 2-3 times baseline noise (2000 - 3000 counts) for the
lowest point on the calibration curve. The highest concentration point on the curve must be below the
saturation point of the detector. Use a maximum response of less that 350,000 - 450,000 counts as a
guideline. Adjust Gain Factor, PMT Voltage and/or sample size accordingly.
18. Baseline Stability: Prior to analysis, especially when analyzing low levels, be certain that the detector
baselines are stable and noise free. For a given gain factor, photomultiplier tube voltage may be adjusted to
insure maximum sensitivity while maintaining a stable, noise-free baseline.
19. Calibration Materials/Standard Curve Construction: Prepare calibration standards with solvent
materials that have minimum or no nitrogen contamination relative to the concentration of nitrogen
anticipated in the sample unknown. Correct for nitrogen contribution from solvent materials and impurity
of nitrogen source material. Do not force the calibration curve through the 0, 0 axis, unnecessarily.
Construct standard concentrations that will yield a calibration curve that is linear and that does not exceed
the dynamic range of the detector [use a correlation coefficient of .999 and 1 order of magnitude (example:
10-100) as a guideline]. The curve should yield an estimated value that can be used to calculate nitrogen
content in the sample on a mass/mass basis.
84
20. Quality Assurance: A quality assurance (Q.A.) sample of known nitrogen content shall be analyzed
after each calibration and at least each day of use thereafter. To establish the statistical control status of the
testing process. Q.A. samples are regularly analyzed as if they were unknown samples. These results are
recorded and immediately analyzed by total testing process. Any out of control data should immediately
trigger investigation for root cause(s). The outcome of the investigation may, but not necessarily, result in
instrument recalibration. Depending on the criticality of the quality being measured, and the demonstrated
stability of the testing process, the frequency of quality assurance recommended that the Q.A. sample(s)
regularly used be representative of the material routinely analyzed and that precision should be checked
against the stated ASTM precision.
21. To preserve volatile components, that may be present in some samples, do not uncover the samples any
longer than necessary.
22. Analyze samples as soon as possible after taking from the bulk supplies to prevent loss of nitrogen, or
contamination due to exposure or contact with sample container.
23. If a test sample is not used immediately, then thoroughly mix it in its container prior to taking a test
specimen. Some samples may require some heating in order to thoroughly homogenize.
24. Since the formation of NO and NOa from oxidative combustion of nitrogen-containing hydrocarbons is
dependent on combustion conditions such as temperature and oxygen concentration, maintain consistent
operation s for both calibration standards and test specimens in steps such as injection of a constant solution
volume, using a common solvent for dilutions of all test specimens and standards and maintaining
consistent combustion conditions.
25. Measure calibration standards, samples and blanks three times each and take the average response.
26. Burn the residual nitrogen out from the quartz boats by going through the combustion sequence. The blank
should be <1 PPM of nitrogen. The cleaning procedure must be repeated whenever the connection of the
boat inlet system to the pyrolysis tube is opened or whenever new quartz wool is placed in the boat.
27. The nitrogen concentration of the test specimen solution must be less than the concentration of the highest
calibration standard; if not, dilute the sample either on a
Nitrogen (Carbon & Hydrogen) by Combustion and Detection: D5291

1. All species of nitrogen can be determined by these methods. Thus, the results may be generally higher than
those obtained by Kjeldahl methods.
2. Results below 0.2 mass % nitrogen obtained by this method cannot be relied upon. In such cases use
D3228, D4629 or D5762 test methods.
3. Column must be periodically replaced: combustion tubes and reduction reactors usually after about 300
samples, and water trap and carbon dioxide trap after about 50 samples.
POUR POINTS OF PETROLEUM PRODUCTS

85
There are several pour point testing methods, one of which is manual measurement, and the others are
automated based on different physical principles on cooling the petroleum product.
ASTM Standard Analysis Page

D97 Manual 81
D5949 Automatic Pressure Pulsing Method 81
D5950 Automatic Tilt Method 82
D5985 Automatic Rotational Method 82
D6892 Automatic Robotic Tilt Method 82
D97: Pour Point by Manual Measurement

1. Thermometers should be checked immediately prior to running the test, and used only if they are accurate
within ±1°C.
2. The samples must be kept at room temperatures for 24 hours before testing, if the thermal history of the
sample is not known or if the sample has been heated to a temperature higher than 45°C during the
preceding 24 hours.
3. Once the sample has cooled to allow the formation of paraffin wax crystals, do not disturb the mass of oil or
permit the thermometer to shift in the sample. .Any disturbance of the spongy network of wax crystals will
give low and erroneous results.
4. For all pour point measurements, add 3°C to the pour point temperature recorded during measurement, and
report that value as the pour point of the sample.
5. Pour points are expressed in integers that are positive or negative multiples of 3°C.
D5949: Pour Point by Automatic Pressure Pulsing Method
1. This test method should not be used for crude oils.
2. Samples of very viscous materials may be warmed until they are reasonably fluid before they are
transferred; however, no sample shall be heated more than is absolutely necessary. The sample shall not be
heated and transferred into the test specimen cup unless its temperature is 70°C or lower. In the event the
sample is heated above this temperature, allow the sample to cool until its temperature is at least 70°C
before transferring.
D5950: Pour Point by Automatic Tilt Method
86
3. Residual fuels are known to be sensitive to thermal history. In the case where a residual fuel is tested, refer
to Test Method D97 for sample treatment.
D5985: Pour Point by Automatic Rotational Method
3. Residual fuels are known to be sensitive to thermal history. In the case where a residual fuel is tested, refer
to Test Method D97 for sample treatment.
D6892: Pour Point by Automatic Robotic Tilt Method
1. This test method should not be used for crude oils. The applicability of this test method has not been
validated for residual fuel sample.
SAPONIFICATION NUMBER OF PETROLEUM PRODUCTS: D94

There are two methods under this designation. Method A is color indicator titration, and Method B is
potentiometric titration.
1. Do not use etched or scratched Erlenmeyer flasks because KOH will react with them. The glassware shall
be chemically clean. It is recommended that flasks be cleaned with chromic acid cleaning solution or
alternatively Nochromix or similar product can be used.
2. Aqueous HCl must be standardized against alcoholic KOH to be able to detect molarity changes of 0.0005.
3. Standardize alcoholic KOH solution against standard potassium hydrogen phthalate.
4. On prolonged storage, alcoholic KOH solution becomes discolored. In such cases it should be discarded.
87
5. It is preferable to prepare the KOH solution from commercially available KOH ampule. This type of
solution gives consistent blanks, and since it does not contain carbonate, it does not give multiple inflection
points.
6. When saponification numbers below 1 are expected, better precision can be obtained by using 0.1 M KOH
and HCl instead of 0.5 molar solutions.
7. Blanks in duplicate must be run with all samples analyzed.
8. If a volumetric pipette is used to measure the alcoholic KOH solution, wait 30 s after delivery to allow for
complete drainage.
9. Use the sample weights suggested in Note 21 of D94 method; but do not exceed 20 g sample limit.
10. Although the standard procedure requires 30 min of reflux, some samples may complete saponification
within 10 min; others may require more than 2 hours. Neither the shortened period nor the longer period
should be used except by mutual consent of interested parties.
11. Pouring 50 mL of naphtha down the condenser at the end of the saponification not only rinses the
condenser but also cools the reaction mixture.
12. For dark colored samples, the potentiometric method is preferred over the colorimetric method to be clearly
able to distinguish the end point.
13. Since on titration, two immiscible phases appear and KCl is precipitated, stirring conditions are critical and
vigorous stirring is essential. Avoid emulsification of the titration mixture by swirling the flask vigorously as
the end point is approached. Use a Teflon coated 2.5 × 0.5 cm stir bar.
14. The titration apparatus may need grounding, if the meter shows erratic movements when approached by an
operator.
15. Cleaning the electrodes thoroughly, keeping the ground-glass joint free of foreign materials, and regularly
testing the electrodes are very important in obtaining repeatable results.
16. At the end of the blank titration and between successive titrations, a thin film of KCl crystal coats the
electrode and the titrant delivery tip. Use a water jet to remove it, and rinse with distilled water.
17. Dry the electrodes by blotting with a paper towel. Do NOT rub the electrodes.
18. At the end of a set of sample titrations, clean the deposited KCl crystals and sample residue, by washing
with water, and then rinsing the electrodes in a beaker of 50 mL Varsol + 38 mL isopropanol + 38 mL
water for a minute. Clean the electrodes further with distilled water and blot-dry with paper towel.
19. Hold the electrodes firmly in a steady holder during the titration. Wobbling electrodes create non-repeatable
results by generating electrical noise.
88
20. Two inflection points may be obtained in the titration curve if the KOH solution is contaminated with a
small amount of potassium carbonate. The first inflection point is from KOH, the second from carbonate.
SODIUM IN RESIDUAL FUEL OIL: D1318
1. Platinum dishes are used in this test method for combustion of the sample. Handle the platinum dish only
with platinum-tipped tongs and do not touch it with fingers during the test. Carefully dust the bottom of the
dish with a clean camel-hair brush before each weighing.
2. If the sample contains appreciable amount of water, as indicated by spattering when heated, add a few mL
of ethanol or iso-propyl alcohol before heating. Include the alcohol in the blank determination.
3. The platinum dishes should be placed on silica plates or silica triangles on the floor of the muffle furnace.
Particular care must be exercised to avoid the contamination of the sample with particles from the roof,
walls, and the door of the furnace. During the initial ignition, the opening of the muffle door must be
carefully adjusted so that the air flow is not excessive. Too great an air flow causes high temperatures in the
burning carbon and also possible loss of ash from dish.
4. The ash is treated with sulfuric and hydrofluoric Acids with heat to remove the HF from the solution.
Unless the silica is removed, low value will result from the occlusion of sodium in the insoluble residue.
Sulfur by General High Pressure Decomposition Device Method: D129
1. This method is not applicable to samples containing metals that give residues which are insoluble in dilute
hydrochloric acid. The test method is also not applicable to used oils.
2. After repeated use of the high pressure decomposition device a film may be noticed on the inner surface.
This dullness can be removed by periodic polishing of the high pressure decomposition device. See Note 3
in the standard.
3. Do not use more than 1 g of total of sample + white oil for ignition in the decomposition device.
4. Make a blank determination whenever new reagents or white oil are used.
SULFUR IN PETROLEUM LIQUIDS BY COMBUSTION

UV-FLUORESCENCE: D5453
1. A correction factor for benzothiophene used as the calibration standard may need a
correction factor for chemical purity.
89
2. Working sulfur standards that simulate or match the composition or matrix of the samples
analyzed can reduce test result bias between analysis.
3. Working standards should be remixed on a regular basis depending on the frequency of use
and age. Typically, stock solutions have a useful life of about 3 months.
4. Calibration standards from commercial sources can be used if checked for accuracy and if
precision is not degraded.
5. To preserve volatile components which are in some samples, do not uncover samples any
longer than necessary. Samples shall be analyzed as soon as possible after taking from the
bulk supplies to prevent loss of sulfur or contamination due to exposure or contact with
sample container.
VOLATILE SULFUR IN GASEOUS HYDROCARBONS AND

LPG BY UV-FLUORESCENCE: D6667
1. Prior to sample injection, fully stabilize and ready the apparatus for analysis according to the
2. Valves in the sample inlet system typically remain in the load position except during sample
analysis.
3. Once the sample valve has been filled and allowed to equilibrate, accomplish sample
injection by executing a prompt and full rotation to the sample valve to the inject position.
4. Leave the sampling valve in the inject position until analysis has been completed (instrument
has returned to baseline and integration has been finished).
5. The length of time required for detector response will depend upon the type of pyrotube used,
carrier gas, sample size, or sulfur concentration, or both. From 20 s to 1 min can be typical.
6. Sample inlet system carrier gas flows can be used to manipulate sample combustion and
detection characteristics. However, excessive carrier flow rates (greater than 30 mL/min) can
cause incomplete sample combustion and resultant sooting.
7. Allow time for return of signal to baseline between injections.
8. For sample cylinders containing LPG, use sufficient pressure (typically greater than 200 psig
container pressure) to allow the transfer of sample to the sample inlet system without the
formation of bubbles in the transfer tubing and sight glass.
9. Use standard gas flow conditions for the analyzer. See section 9 of the test method.
10. The use of a filtering device prior to sample introduction is strongly recommended. This can
90
greatly extend valve service and prevent transfer line tubing blockage.
11. The use of low or iron-free alloys and/or inert treated materials can enhance the analysis for
low level sulfur contamination.
12. The use of a strip-chart recorder or a software peak display can aid in the set up and normal
operation of the sample inlet system.
13. Quality analytical results are best obtained when calibration materials match the matrix of the
samples analyzed. Injection of solvent (liquids at room temperature) as calibrants or samples
is discouraged and can cause severe coking or sooting of sample flow path components and
yield poor results.
Reid Vapor Pressure of Petroleum Products: D323
1. Gross errors can be obtained in vapor pressure measurements if the prescribed procedure is
not followed carefully, particularly emphasizing the checking of the pressure gauge,
checking for leaks, sampling, purging the apparatus, coupling the apparatus, and shaking the
apparatus.
2. The Reid vapor pressure determination shall be performed on the first test specimen
withdrawn from the sample container. The remaining sample in the container cannot be used
for a second vapor pressure determination. If necessary, obtain a new sample.
3. Protect samples from excessive heat prior to testing.
4. Do not test samples in leaky containers. They should be discarded and new samples obtained.
5. In all cases, cool the sample container and contents to 0 to 1°C before the container is
opened.
YIELD STRESS AND APPARENT VISCOSITY USING MINI

ROTARY VISCOMETER (MRV) TEST: D4684
This test measures yield stress and apparent viscosity of engine oils after cooling at a controlled
rate over a period exceeding 45 hours to a final temperature between -10 and -40°C. This test
method is applicable to fresh engine oils and used and fresh diesel engine oils.
1. There are two procedures in this standard. Procedure A is the new procedure, and procedure
B is the original earlier version of the test.
2a. Procedure A incorporates several equipment and procedural modifications from test method
D4684-02 version. It utilizes thermoelectric cooling or indirect refrigeration technology of
recent manufacture. It has improved precision over the older procedure.
91
2b. Procedure B can use the same instrument used in procedure A or those with circulating
methanol as a coolant.
3. Temperature controller is a very critical part of this procedure.
4. If the sample in the container is below the dew point temperature of the room, warm the
sample to room temperature before opening the can.
5. The temperature sensor controller shall be verified at a minimum of three temperatures (at
least 5°C apart and include -5°C and lowest test temperature to prepare a calibration curve)
using a reference thermometer.
6. Make at least two temperature measurements at every calibration temperature with at least 10
min between observations.
7. Determine the calibration constant of each rotor/stator combination by conducting 2 tests at -

25°C using a viscometric reference standard.
8. Calibrate the each cell twice and calculate the calibration constant from the average of the
two determinations of the time for 3 revolutions of the rotor.
9. The same 150 g weight or different weights certified to be 150 ± 0.1 g should be used for
both calibration and viscosity measurements.
10. The thermometer or the TMD must be placed into the same thermowell for all measurements,
at least 1 hour prior to completion of the test.
11. Two TMDs are required: one in +70 to 90°C in 1°C subdivisions, and a second in 0.2°C
subdivisions from +5 to -41°C range.
12. The simplest way to check a liquid in glass thermometer calibration is to check its ice point.
13. If the final temperature differs by 0.2°C from programmed temperature, check:
- TMD calibration
- Temperature sensor for accuracy
- Adequate amount of coolant and that it is flowing
- Replace methanol if wet as indicated by ice crystals on top
- Change methanol monthly
- Check that the refrigeration system is properly working
- Check profile—manually programmed or custom made
- Check for errors in temperature profile and correct
- Verify preheat program for 80°C that it lasts at least for two hours.
14. Use only dry filtered air; not house air which may contain oil, water or other contaminants.
92
15. Do all measurements beginning with the cell farthest to the left facing the instrument.
16. If the calibration constant of any cell differs by more than 4 % from the average of all cells,
then one or both of the results are suspect. If so, examine the indicated rotor for damage,
repair, or replacement as necessary. Repeat all cell calibrations.
17. All cells (even unused ones) should contain a fluid and a rotor. If there are less than a full set
of samples to run, fill each of the unused cells with a typical test sample.
CLEANING
18. After the measurements, clean the cells after the instrument warms up to the room
temperature or somewhat above it. Do not clean the cells above a temperature of 55°C.
19. Rinse the cells at least 3 times with about 15 mL of an appropriate solvent for each rinse,
followed by a rinse with acetone.
20. Remove the traces of residual solvent by flushing the cell with dry air or with a vacuum hose.
Since the house air is frequently contaminated with oil, water, etc., it is preferable to use
clean air or a vacuum.
REPORTING
21. Yield Stress—Report as less than the value at which rotation was observed.
22. Apparent Viscosity—Report as follows:
If viscosity is (mPa.s) Report as or to the nearest (mPa.s)

< 5000 < 5000
5000 – 100 000 100
100 000 – 400 000 1000
 400 000  400 000
If the rotor did not move with 150 g weight report as “too viscous to measure”.
PROCEDURE B
23. For cold sources operating below -20°C, replace methanol if wet, as indicated by ice crystals
in the top of the cold source reservoir. In the high humidity areas, it may be necessary to
change the methanol once a month.
93
24. Check to see that the refrigeration system is working properly. Use the instrument manual
and advise from the bath manufacturer should be utilized.
25. The sensed temperature shall be verified using a reference thermometer at a minimum of 3
temperatures. Make these measurements at least 5°C apart.
26. The MRV block and the oil in the cells should be soaked in oil at -20 ± 0.2°C for at least an
hour starting the program.
27. Repeat the cell calibrations from left to right.
28. If any cell calibration constant differs by 10% from the average of all test cells, check the
rotor for damage, and recalibrate the instrument.
CLEANING
29. After all cells have been completed, exit the cooling program and turn on the heater to warm
the cells to room temperature or somewhat higher, but not exceeding 50°C.
30. With a vacuum, remove the oil samples and rinse the cells with an oil solvent several times,
followed by two washings with acetone. Use a vacuum to remove the solvent after each
rinse, and allow acetone to evaporate to dryness after the final rinse.
REPORTING
31. For unused oils, report the final test temperature and either the apparent viscosity or the
existence of yield stress, but NOT both.
32. Report yield stress as less than the value at which rotation was observed.
33. Report as follows:
If viscosity is (mPa.s) Report as or to the nearest (mPa.s)

< 5000 < 5000
5000 – 100 000 100
100 000 – 400 000 1000
 400 000  400 000
34. If the instrument software provides 3 viscosity values, the first value shall be reported as the
apparent viscosity. Never report an average value of 3 measurements, but all 3 values may be
reported in sequence.
WATER IN CRUDE OIL: D4377

94
1. A number of compounds interfere with this titration, similar to other Karl Fischer titrations.
The most common interferences are mercaptans and sulfides. At levels of less than 500
mg/kg (as sulfur) these interferences are insignificant.
2. The precision of this test method is critically dependent on the effectiveness of the
homogenization step given in Annex A1 of the standard. The type of mixer used depends on
the quantity of crude oil to be homogenized. Before any unknown mixer is used, the
specifications for the homogenization test given in Annex A1 must be met.
3. Re-evaluate the mixer for any changes in the type of crude oil, the volume of the crude oil in
the container, the shape of the container, or the mixing conditions.
4. Mix the test sample of crude oil immediately (within 15 min) before analysis to ensure
complete homogeneity. Mix the test sample at room temperature (25°C or less) in the
original container. Mixing of the sample should not raise the temperature of the sample more
than 10°C, or a loss of water may occur. The type of mixer depends on the quantity of the
crude oil. The specifications of the mixer need to meet the specifications given in Annex A1
of this test method.
5. All equipment must be scrupulously clean of moisture. Rinse all syringes, needles, and
weighing bottles with anhydrous acetone after cleaning. Then dry in an oven at 100°C for at
least an hour, and store immediately in a desiccator.
6. Fill the dry cooled sample bottle as rapidly as possible with the sample within a ½ inch of the
top and immediately seal.
7. After removing a sample aliquot from the bottle with a hypodermic syringe, inject dry
nitrogen into the sample bottle to displace the removal of the sample void.
8. Standardize the Karl Fischer reagent with distilled water at least once daily. After adding
water don not shake the cell. When wiping the needle exercise care, so as not to siphon the
liquid through the needle tip.
9. The sample solvent should be changed when the sample content exceeds 2 g of crude oil per
15 mL of solvent or when 4 mL of titrant per 15 mL of solvent has been added to the titration
vessel.
Water in Petroleum Products by Coulometry: D6304
1. A number of chemicals interfere in this titration: mercaptans, sulfides, amines, ketones,

aldehydes, oxidizing and reducing agents, and so forth. Some of the interferences can be
eliminated by addition of suitable reagents, e.g., addition of benzoic or succinic acid for
aldehyde and ketone interference.
2. At low water concentrations (<0.02 mass %),the interference by mercaptan and sulfide (>500
mg/kg as sulfur) may be significant (see Test Method E203).
95
3. All equipment should be scrupulously clean of moisture. Rinse all syringes, needles, and
weighing bottles with anhydrous acetone after cleaning. Then dry in an oven at 100°C for at
least an hour and store immediately in a desiccator.
4. Fill the dry cooled sample bottle as rapidly as possible with the sample within 15 mm of the
top and seal immediately.
5. After removing a sample aliquot from the bottle with a dry hypodermic syringe, inject dry
nitrogen into the sample bottle with the syringe to displace the removed sample void.
6. The presence of gas bubbles in the syringe may be a source of uncertainty. Viscous samples
may be difficult to measure with a precision syringe. In such cases, taking the sample aliquot
by mass is preferred to volume measurement.
7. Although standardization is not necessary in coulometric titrations, reagent performance

deteriorates with use and must be regularly monitored by accurately injecting 10 000 µg or
10 µL of pure water. Suggested intervals are initially with fresh reagents and then after every
ten determinations.
8. Rinse the clean dry syringe at least three times with the sample and discard the aliquots
before taking an aliquot for injecting into the titration vessel.
9. During the blank measurement instrument preparation, high background current for a
prolonged period may be due to moisture on the inside walls of the titration vessel. Wash the
inside with electrolyte by gently shaking the vessel or by more vigorously stirring.
10. The frit separating the vessel compartments may get clogged with sample residues;
Disassemble the apparatus in such cases and acid clean the frit.
11. Any time one of the following situations occurs, replace the anode and the cathode solutions,
and then repeat the preparation of the apparatus as given in Section 9 of the test method.
11a. Persistently high and unstable background current.
11b. Phase separation in the anode compartment or the sample coating the electrodes.
11c. The total amount of sample added to the titration vessel exceeds one fourth of the
volume of solution in the anode compartment.
11.d The solutions in the titration vessel are over one week old.
11e. The instrument displays error messages that suggest replacement of the electrodes.
11f. The results of a 10 µL injection of water is outside 10 000 ± 200 µg.

96
12. If the titration vessel gets contaminated with the sample, thoroughly clean the anode and the
cathode compartments with xylene. Never use acetone or similar ketones.

ASTM D02 Committee Petroleum Testing Aids

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COMMITTEE D02 ON PETROLEUM PRODUCTS, LIQUID FUELS, AND LUBRICANTS

D4684 Yield Stress and Apparent Viscosity Petroleum Products 91

Analysis Test Method Page

Metals in Crude Oils by AAS D5863 44

ACID NUMBERS BY TITRATIONS

Acid Number of Petroleum Products by

Acid and Base Number by Color Indicator Titration: D974

1. Same notes as # 1, 2, 3, 4, 8, and 9 above for Test Method D664.

Acid Number of Petroleum Products by Semi-Micro

APPARENT VISCOSITY USING COLD CRANKING

ASH FROM PETROLEUM PRODUCTS: D482

5a. Do not leave the burning samples unattended by the operator.

7a. All crucibles should be weighed as soon as they have cooled.

SULFATED ASH FROM LUBRICATING

5. Check the ashing furnace periodically to assure a temperature of 775 ± 25°C.

BASE NUMBERS OF PETROLEUM PRODUCTS BY

D2896: Perchloric Acid Titration

D4739: Hydrochloric Acid Titration

1. All comments above for D2896 also apply to D4739.

3. Alcoholic KOH must be standardized frequently enough to detect normality changes of

BROOKFIELD VISCOSITY OF LUBRICANTS: D2983

2. Thermometer or other temperature indicator device must be calibrated against a master

4. It is a good laboratory practice to store spindles in a protective manner. Do not leave

7. Maintenance of proper immersion depth is essential to getting good precision. An immersion

Chlorine in New and Used Petroleum Products: D808

1. Do not used decomposition pressure vessels with scratched inner surfaces.

2. A white oil blank must be run throughout the procedure.

5. Protect the silver chloride precipitate from light.

CLOUD POINT OF PETROLEUM PRODUCTS

ASTM Standard Analysis

D2500: Cloud Point of Petroleum Products

3. Maintain the temperature of the cooling bath at 0 ± 1.5°C.

D5771: Cloud Point by Optical Detection Stepped Cooling Method

D5772: Cloud Point by Linear Cooling Rate Method

D5773: Cloud Point by Constant Cooling Rate Method

D7689: Cloud Point by Mini Method

COLOR MEASUREMENT OF PETROLEUM PRODUCTS

D1500: ASTM COLOR SCALE

2. In such case, report the result as L (darker glass), e.g., L7.5

4. Do not report the color than in 0.5 units.

DENSITY AND GRAVITY OF PETROLEUM PRODUCTS

D287: API Gravity of Crude Petroleum and Petroleum Products

2. Use hydrometers supplied with a calibration certificate.

3. Thermometers must be calibrated against a master thermometer at least once a year.

D1298: Density, Relative Density, or API Gravity of Crude

D4052: Density, Relative Density, and API Gravity of Liquids by

D5002: Density and Relative Density of Crude Oil by Digital Density

ETHANOL AND METHANOL IN FUELS BY GC: D5501

EVAPORATION LOSS OF LUBRICATING

5. Cleaning at regular intervals of foreign material adhering on exhaust system parts,

17. If the extraction tube is loose, tighten or check the gasket.

D56: Flash Point by Tag Closed Cup Tester

3. Observed flash point obtained must be corrected for barometric pressure.

D92: Flash And Fire Points by Cleveland Open Cup Tester

D93: Flash Point by Pensky-Martens Closed Cup Tester

4. Temperature measuring devices could be thermometer or electronic. If a thermometer is

NIST CRM MATERIAL FLASH POINT, °C

D3828: Flash Point by Seta Small Scale Closed Cup Tester

3. More frequent checking with a secondary working standard

Foaming Characteristics of Lubricating Oils: D892