Designation: D6417 − 09

Standard Test Method for

Estimation of Engine Oil Volatility by Capillary Gas
Chromatography1
This standard is issued under the fixed designation D6417; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope* 2. Referenced Documents

1.1 This test method covers an estimation of the amount of 2.1 ASTM Standards:2
engine oil volatilized at 371°C (700°F). D2887 Test Method for Boiling Range Distribution of Pe-
1.1.1 This test method can also be used to estimate the troleum Fractions by Gas Chromatography
amount of oil volatilized at any temperature between 126 and D4626 Practice for Calculation of Gas Chromatographic
371°C, if so desired. Response Factors
1.2 This test method is limited to samples having an initial D5800 Test Method for Evaporation Loss of Lubricating
boiling point (IBP) greater than 126°C (259°F) or the first Oils by the Noack Method
calibration point and to samples containing lubricant base oils E355 Practice for Gas Chromatography Terms and Relation-
with end points less than 615°C (1139°F) or the last n-paraffins ships
in the calibration mixture. By using some instruments and E594 Practice for Testing Flame Ionization Detectors Used
columns, it is possible to extend the useful range of the test in Gas or Supercritical Fluid Chromatography
method. E1510 Practice for Installing Fused Silica Open Tubular
Capillary Columns in Gas Chromatographs
1.3 This test method uses the principles of simulated distil-
lation methodology. 2.2 Coordinating European Council Standard:
CEC L-40–93 Evaporation Loss of Lubricating Oils (NO-
1.4 This test method may be applied to both lubricant oil ACK Evaporative Tester)3
base stocks and finished lubricants containing additive pack-
ages. These additive packages generally contain high molecu- 3. Terminology
lar weight, nonvolatile components that do not elute from the
chromatographic column under the test conditions. The calcu- 3.1 Definitions—This test method makes reference to many
lation procedure used in this test method assumes that all of the common gas chromatographic procedures, terms, and relation-
sample elutes from the column and is detected with uniform ships. Detailed definitions of these can be found in Practices
response. This assumption is not true for samples with non- E355, E594, and E1510.
volatile additives, and application of this test method under 3.2 Definitions of Terms Specific to This Standard:
such conditions will yield results higher than expected. For this 3.2.1 area slice—the area resulting from the integration of
reason, results by this test method are reported as area percent the chromatographic detector signal within a specified reten-
of oil. tion time interval. In area slice mode (see 6.5.2), peak detection
1.5 The values stated in SI units are to be regarded as parameters are bypassed and the detector signal integral is
standard. The values stated in inch-pound units are provided recorded as area slices of consecutive, fixed duration time
for information only. intervals.
1.6 This standard does not purport to address all of the 3.2.2 corrected area slice—an area slice corrected for base-
safety concerns, if any, associated with its use. It is the line offset by subtraction of the exactly corresponding area
responsibility of the user of this standard to establish appro- slice in a previously recorded blank (nonsample) analysis.
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use.
2
For referenced ASTM standards, visit the ASTM website, [Link], or
1
This test method is under the jurisdiction of ASTM Committee D02 on contact ASTM Customer Service at service@[Link]. For Annual Book of ASTM
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee Standards volume information, refer to the standard’s Document Summary page on
D02.04.0H on Chromatographic Distribution Methods. the ASTM website.
3
Current edition approved June 1, 2009. Published June 2009. Originally Available from Coordinating European Council (CEC), C/o Interlynk Admin-
approved in 1999. Last previous edition approved in 2003 as D6417–03. DOI: istrative Services, Ltd., P.O. Box 6475, Earl Shilton, Leicester, LE9 9ZB, U.K.,
10.1520/D6417-09. [Link]

*A Summary of Changes section appears at the end of this standard

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

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 D6417 − 09
3.2.3 cumulative corrected area—the accumulated sum of this test method can be biased by the presence of additives
corrected area slices from the beginning of the analysis through (polymeric materials), which may not completely elute from
a given retention time (RT), ignoring any nonsample area (for the gas chromatographic column, or by heavier base oils not
example, solvent). completely eluting from the column. The results of this test
3.2.4 slice rate—the time interval used to integrate the method may also not correlate with other oil volatility methods
continuous (analog) chromatographic detector response during for nonhydrocarbon synthetic oils.
an analysis. The slice rate is expressed in hertz (for example, 5.3 This test method can be used on lubricant products not
integrations or slices per second). within the scope of other test methods using simulated distil-
3.2.5 slice time—the cumulative slice rate (analysis time) lation methodologies, such as Test Method D2887.
associated with each area slice throughout the chromatographic
analysis. The slice time is the time at the end of each 6. Apparatus
contiguous area slice. 6.1 Chromatograph—The gas chromatographic system used
3.2.6 total sample area—the cumulative corrected area from must have the following performance characteristics:
the initial point to the final area point. 6.1.1 Column Oven, capable of sustained and linear pro-
3.3 Abbreviations—A common way to abbreviate hydrocar- grammed temperature operation from near ambient (for ex-
bon compounds is to designate the number of carbon atoms in ample, 35 to 50°C) up to 400°C.
the compound. A prefix is used to indicate the carbon chain 6.1.2 Column Temperature Programmer—The chromato-
form while a subscript suffix denotes the number of carbon graph must be capable of linear programmed temperature
atoms (for example, normal decane n-C10; iso-tetradecane = operation up to 400°C at selectable linear rates up to 20°C/min.
i-C14). The programming rate must be sufficiently reproducible to
obtain the RT repeatability of 0.1 min (6 s) for each component
4. Summary of Test Method in the calibration mixture described in 7.6.
6.1.3 Detector—This test method requires a FID. The de-
4.1 A nonpolar open tubular (capillary) gas chromato-
tector must meet or exceed the following specifications as
graphic column is used to elute the hydrocarbon components of
detailed in Practice E594.
the sample in order of increasing boiling point.
[Link] Operating Temperature, up to 400°C.
4.2 A sample aliquot is diluted with a viscosity reducing [Link] Sensitivity, >0.005 coulombs/g carbon.
solvent and introduced into the chromatographic system. At [Link] Minimum Detectability, 1 × 10−11 g carbon / s.
least one laboratory analyzed samples using neat injection [Link] Linear Range, 106.
without solvent dilution. The precision of the method was [Link] Connection of the column to the detector must be
calculated on diluted samples. If a laboratory chooses to use such that no temperature below the column temperature exists.
neat injection, it should first confirm that it is obtaining similar Refer to Practice E1510 for proper installation and condition-
results. Sample vaporization is provided by separate heating of ing of the capillary column.
the point of injection or in conjunction with column oven 6.1.4 Sample Inlet System—Any sample inlet system ca-
heating. pable of meeting the performance specification in 7.6 may be
4.3 The column oven temperature is raised at a reproducible used. Programmed temperature vaporization (PTV) and pro-
linear rate to effect separation of the hydrocarbon components grammable cool on-column injection systems have been used
in order of increasing boiling point. The elution of sample successfully.
components is quantitatively determined by a flame ionization 6.2 Microsyringe—A microsyringe with a 23 gage, or
detector (FID). The detector signal integral is recorded as area smaller, stainless steel needle is used for on-column sample
slices for consecutive RT intervals during the analysis. introduction. Syringes of 0.1 µL to 10 µL capacity have been
4.4 RTs of known hydrocarbons spanning the scope of the used.
test method (C8-C60) are determined and correlated to their 6.2.1 Automatic syringe injection is recommended to
boiling point temperatures. The RT at 371°C (700°F) is achieve best precision.
calculated using linear regression, utilizing the calibration 6.3 Column—This test method is limited to the use of
developed from the n-paraffins. The cumulative corrected area nonpolar wall coated open tubular (WCOT) columns of high
of the sample determined to the 371°C RT is used to calculate thermal stability. Glass, fused silica, and stainless steel col-
the percentage of oil volatilized at 371°C. umns with a 0.53-mm diameter have been successfully used.
Cross-linked or bonded methyl silicone liquid phases with film
5. Significance and Use thickness from 0.10 to 1.0 µm have been used. The column
5.1 The determination of engine oil volatility at 371°C length and liquid phase film thickness must allow the elution of
(700°F) is a requirement in some lubricant specifications. at least C60 n-paraffin (boiling point = 615°C). The column
5.2 This test method is intended as an alternative to Test and conditions must provide separation of typical petroleum
Methods D5800 and the Noack method for the determination hydrocarbons in order of increasing boiling point and meet the
of engine oil volatility (CEC L-40–93). The data obtained from column resolution requirements of 8.2.1.
this test method are not directly equivalent to Test Method 6.4 Carrier Gas Flow/Pressure Control—The optimum car-
D5800. The calculated results of the oil volatility estimation by rier gas flow for the column and chromatographic system

Copyright by ASTM Int'l (all rights reserved); 2

 D6417 − 09
should be used. It is recommended that the system be equipped of n-paraffin mixture to 100 parts of solvent. It is recommended
with a constant pressure/constant flow device capable of that at least one compound in the mixture have a boiling point
maintaining the carrier gas at a constant flow rate throughout lower than the IBP of the sample being analyzed, as defined in
the temperature program. the scope of this test method (see 1.1). It is recommended that
6.5 Data Acquisition System: the calibration mixture contain at least eleven known
6.5.1 Recorder—A 0 to 1 mV range recording potentiom- n-paraffins (for example, C8, C9, C10, C12, C16, C20, C30, C40,
eter, or equivalent, with a full-scale response time of 2 s, or C50, C52 and C60). Boiling points of n-paraffins are listed in
less, may be used to provide a graphical display. Table 1.
6.5.2 Integrator—Means must be provided for determining NOTE 2—A suitable calibration mixture can be obtained by dissolving
the accumulated area under the chromatogram. This can be a synthetic wax in a volatile solvent (for example, carbon disulfide or
done by means of an electronic integrator or computer based cyclohexane). Solutions of 1 part synthetic wax to 200 parts solvent can
chromatography data system. The integrator/computer system be prepared. Lower boiling point paraffins will have to be added to ensure
conformance with 7.5.
must have normal chromatographic software for measuring the
retention time and areas of eluting peaks (peak detection 7.7 Response Linearity Mixture—Prepare a quantitatively
mode). In addition, the system must be capable of converting weighed mixture of about ten individual paraffins (>99 %
the continuously integrated detector signal into area slices of purity), covering the boiling range of the test method. The
fixed duration (area slice mode). These contiguous area slices, highest boiling point component should be at least n-C60. The
collected for the entire analysis, are stored for later processing. mixture must contain n-C40. Use a suitable solvent to provide
The electronic range of the integrator/computer (for example, 1 a solution of each component at approximately 0.5 % to 2.0 %
V, 10 V) must be within the linear range of the detector/ by mass.
electrometer system used.
8. Preparation of Apparatus
NOTE 1—Some gas chromatographs have an algorithm built into their
operating software that allows a mathematical model of the baseline 8.1 Gas Chromatograph Setup:
profile to be stored in memory. This profile is automatically subtracted
from the detector signal on subsequent sample runs to compensate for the 8.1.1 Place the gas chromatograph and ancillary equipment
column bleed. Some integration systems also store and automatically into operation in accordance with the manufacturer’s instruc-
subtract a blank analysis from subsequent analytical determinations. tions. Recommended operating conditions are shown in Table
2.
7. Reagents and Materials 8.1.2 When attaching the column to the detector inlet,
7.1 Carrier Gas—Helium, nitrogen, or hydrogen of high ensure that the end of the column terminates as close as
purity. (Warning —Helium and nitrogen are compressed gases possible to the FID jet. Follow the instructions in Practice
under high pressure. Hydrogen is an extremely flammable gas E1510.
under high pressure.) Additional purification is recommended 8.1.3 The FID should be periodically inspected and, if
by the use of molecular sieves or other suitable agents to necessary, remove any foreign deposits formed in the detector
remove water, oxygen, and hydrocarbons. Available pressure from combustion of silicone liquid phase or other materials.
must be sufficient to ensure a constant carrier gas flow rate. Such deposits will change the response characteristics of the
7.2 Hydrogen—Hydrogen of high purity (for example, hy- detector.
drocarbon free) is used as fuel for the FID. (Warning— 8.1.4 The inlet liner and initial portion of the column must
Hydrogen is an extremely flammable gas under high pressure.) be periodically inspected and replaced, if necessary, to remove
extraneous deposits or sample residue.
7.3 Air—High purity (for example, hydrocarbon free) com-
pressed air is used as the oxidant for the FID. (Warning— 8.1.5 Column Conditioning—A new column will require
Compressed air is a gas under high pressure and supports conditioning at the upper test method operating temperature to
combustion.) reduce or eliminate significant liquid phase bleed, resulting in
a stable chromatographic baseline. Follow the guidelines
7.4 Carbon Disulfide (CS2) (99+ % pure), may be used as a outlined in Practice E1510.
viscosity reducing solvent. It is miscible with asphaltic hydro-
carbons and provides relatively little response with the FID. 8.2 System Performance Specification:
The quality (hydrocarbon content) should be determined by 8.2.1 Column Resolution—The column resolution, influ-
this test method prior to use as a sample diluent. (Warning— enced by both the column’s physical parameters and operating
Carbon disulfide is extremely flammable and toxic.) conditions, affects the overall determination of boiling range
distribution. Resolution is therefore specified to maintain
7.5 Cyclohexane—(99+ % pure), may be used as a viscosity
equivalence between different systems (laboratories) employ-
reducing solvent. It is miscible with asphaltic hydrocarbons;
ing this test method. Resolution is determined using Eq 1 and
however, it responds well to the FID. The quality (hydrocarbon
the C50 and C52 paraffins from a calibration mixture analysis
content) should be determined by this test method prior to use
(see 7.6). Resolution ( R) should be at least one, using the
as a sample diluent. ( Warning—Cyclohexane is flammable.)
identical conditions employed for sample analyses.
7.6 Calibration Mixture—A qualitative mixture of
R 5 2 ~ t 2 2 t 1 / ~ 1.699 ~ w 2 1w 1 !! (1)
n-paraffins (nominally C8 to C60) dissolved in a suitable
solvent. The final concentration should be approximately 1 part where:

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 D6417 − 09
TABLE 1 Boiling Points of n-ParaffinsA,B TABLE 2 Recommended Operating Conditions
Carbon Boiling Boiling Carbon Boiling Boiling Injector Cool on-column or equivalent
Number Point °C Point °F Number Point °C Point °F
2 −89 −127 52 584 1083 Injection temperature oven-track mode
3 −42 −44 53 588 1090
4 0 31 54 592 1098 Auto sampler required for best precision
5 36 97 55 596 1105
6 69 156 56 600 1112 Data collection data is collected as independent area slices
7 98 209 57 604 1119 (average data collection rate is 3 slices per s)
8 126 258 58 608 1126
9 151 303 59 612 1134 Column Capillary, 5 m × 0.53 mm id
10 174 345 60 615 1139 film thickness; 0.1 to 1.0 µm (polymethylsiloxane)
11 196 385 61 619 1146
12 216 421 62 622 1152 Flow conditions UHP helium at 12 mL/min (constant flow) or optimized
13 235 456 63 625 1157 for the column (make-up gas helium at 18 mL/min)
14 254 488 64 629 1164
15 271 519 65 632 1170 Detector Flame Ionization;
16 287 548 66 635 1175 Temperature: 390°C
17 302 576 67 638 1180
18 316 601 68 641 1186 Oven program initial oven temperature 50°C,
19 330 625 69 644 1191 initial hold 0 min,
20 344 651 70 647 1197 program rate 10°C/min,
21 356 675 71 650 1202 final oven temperature 380°C,
22 369 696 72 653 1207 final hold 12 min,
23 380 716 73 655 1211 equilibration time 2 min
24 391 736 74 658 1216
25 402 755 75 661 1222 Sample size 1 µL
26 412 774 76 664 1227
27 422 791 77 667 1233 Sample dilution 2 mass % in carbon disulfide
28 431 808 78 670 1238
29 440 824 79 673 1243 Calibration dilution 1 mass % in carbon disulfide
30 449 840 80 675 1247
31 458 856 81 678 1252
32 466 870 82 681 1258
33 474 885 83 683 1261 R = resolution,
34 481 898 84 686 1267
35 489 912 85 688 1270
t1 = time (s) for the n-C50 peak maximum,
36 496 925 86 691 1276 t2 = time (s) for the n-C52 peak maximum,
37 503 937 87 693 1279 w1 = peak width (s), at half height, of the n-C50 peak, and
38 509 948 88 695 1283 w2 = peak width (s), at half height, of the n-C52 peak.
39 516 961 89 697 1287
40 522 972 90 700 1292 8.2.2 Detector Response Calibration —This test method
41 528 982 91 702 1296
42 534 993 92 704 1299
assumes that the FID response to petroleum hydrocarbons is
43 540 1004 93 706 1303 proportional to the mass of individual components. This must
44 545 1013 94 708 1306 be verified when the system is put in service and whenever any
45 550 1022 95 710 1310
46 556 1033 96 712 1314
changes are made to the system or operational parameters.
47 561 1042 97 714 1317 Analyze the response linearity mixture (see 7.7), using the
48 566 1051 98 716 1321 identical procedure to be used for the analysis of samples (see
49 570 1058 99 718 1324
50 575 1067 100 720 1328
Section 9). Calculate the relative response factor for each
51 579 1074 n-paraffin (relative to n-tetracontane) as per Practice D4626
A
API Project 44, October 31, 1972 is believed to have provided the original normal and Eq 2:
paraffin boiling point data that are listed in Table 1. However, over the years some
of the data contained in both API Project 44 (Thermodynamics Research Center
F n 5 ~ M n /A n ! / ~ M 40/A 40! (2)
Hydrocarbon Project) and D6417 have changed and they are no longer equivalent.
Table 1 represents the current normal paraffin boiling point values accepted by
where:
Subcommittee D02.04 and found in all test methods under the jurisdiction of Fn = relative response factor,
Section D02.04.0H. Mn = mass of the n-paraffin in the mixture,
B
D6417 has traditionally used n-paraffin boiling points rounded to the nearest
whole degree for calibration. The boiling points listed in Table 1 are correct to the An = peak area of the n-paraffin in the mixture,
nearest whole number in both degrees Celsius and degrees Fahrenheit. However, M40 = mass of the n-tetracontane in the mixture, and
if a conversion is made from one unit to the other and then rounded to a whole A40 = peak area of the n-tetracontane in the mixture.
number, the results will not agree with the table values for a few carbon numbers.
For example, the boiling point of n-heptane is 98.425°C, which is correctly rounded The Fn of each n-paraffin should not deviate from unity by
to 98°C in the table. However, converting 98.425°C gives 209.165°F, which rounds more than 6 5 %.
to 209°F, while converting 98°C gives 208.4°F, which rounds to 208°F. Carbon
numbers 2, 4, 7, 8, 9, 13, 14, 15, 16, 25, 27, and 32 are affected by rounding. 8.2.3 Column Temperature—The column temperature pro-
gram profile is selected such that there is separation between

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 D6417 − 09
the solvent and the first n-paraffin peak (n-C8) in the calibration additive package not be run in the sample batch as engine oils.
mixture and the maximum boiling point (615°C) n-paraffin Run a solvent blank after each batch of engine oil samples.
(n-C60) is eluted from the column before reaching the end of NOTE 3—If automatic baseline correction (see Note 1) is provided by
the temperature program. The actual program rate used will be the gas chromatograph, further correction of area slices may not be
influenced by other operating variables, such as column dimen- required. However, if an electronic offset is added to the signal after
sions, carrier gas and flow rate, and sample size. baseline compensation, additional area slice correction may be required in
8.2.4 Column Elution Characteristics —The recommended the form of offset subtraction. Consult the specific instrumentation
instructions to determine if an offset is applied to the signal. If the
column liquid phase is a nonpolar phase, such as 100 % methyl algorithm used is unclear, examine the slice area data to determine if
silicone. further correction is necessary. Determine if any offset has been added to
the compensated signal by examining the corrected area slices of those
9. Procedure time slices that precede the elution of any chromatographic unretained
substance. If these corrected area slices (representing the true baseline)
9.1 Analysis Sequence Protocol —Define and use a prede- deviate from zero, subtract the average of these corrected area slices from
termined schedule of analysis events designed to achieve each corrected area slice in the analysis.
maximum reproducibility for these determinations. Include in
9.4 Retention Time Versus Boiling Point Calibration—A RT
the schedule: cooling the column oven and injector to the initial
versus boiling point calibration must be performed with each
starting temperature, equilibration time, sample injection and
batch of samples analyzed. Inject an appropriate aliquot (0.2 to
system start, analysis, and final temperature hold time. See
2.0 µL) of the calibration mixture (7.6) into the chromatograph,
Table 2 for typical conditions.
using the analysis sequence protocol. Obtain a normal (peak
9.1.1 After chromatographic conditions have been set to
detection) data record to determine the peak RTs and the peak
meet performance requirements, program the column tempera-
areas for each component. Collect a time slice area record if a
ture upward to the maximum temperature to be used and hold
boiling range distribution report is desired. Fig. 1 illustrates a
that temperature for the selected time. Following the analysis
graphical plot of a calibration analysis.
sequence protocol, cool the column to the initial starting
temperature. 9.4.1 Inspect the chromatogram of the calibration mixture
9.1.2 During the cool down and equilibration time, ready for evidence of skewed (non-Gaussian shaped) peaks. Skew-
the integrator/computer system. If a RT calibration is being ness is often an indication of overloading the sample capacity
performed, use the peak detection mode. For samples and of the column, which will result in displacement of the peak
baseline compensation (with or without solvent injection), use apex relative to nonoverloaded peaks. Distortion in RT mea-
the area slice mode operation. This is not necessary if the surement and, hence, errors in boiling point temperature
calculations are done using peak integration software as in calibration will be likely if column overloading occurs. The
10.3.2. The recommended slice rate for this test method is 5.0 column liquid phase loading has a direct bearing on acceptable
Hz (5 slices per second). Other slice rates may be used if within sample size. Reanalyze the calibration mixture using a smaller
the limits of 0.02 and 0.2 % of the RT of the final calibration sample size or a more dilute solution to avoid peak distortion.
component (C60). Other slice rates may be used, as may be 9.4.2 Prepare a calibration table based upon the results of
required for other reasons, if provision is made to accumulate the analysis of the calibration mixture by recording the time of
(bunch) the slice data to within these limits prior to determi- each peak maximum and the boiling point temperature in
nation of the boiling range distribution. degrees Celsius (or Fahrenheit) for every component in the
9.1.3 At the exact time set by the schedule, inject either the mixture. n-Paraffin boiling point temperatures are listed in
calibration mixture, solvent, or sample into the chromatograph; Table 1. An example of a typical calibration report, showing
or make no injection (baseline blank). At the time of injection, RTs and boiling points for each n-paraffin, is found in Table 3.
start the chromatograph time cycle and the integrator/computer 9.5 Sample Preparation—Introduce sample aliquots into the
data acquisition. Follow the analysis protocol for all subse- gas chromatograph as a solution in a suitable solvent (for
quent repetitive analyses or calibrations. Since complete reso- example, CS2 or cyclohexane).
lution of sample peaks is not expected, do not change the 9.5.1 Place approximately 0.1 to 1 g of the sample aliquot
sensitivity setting during the analysis. into a screw-capped or crimp-cap vial.
9.2 Baseline Blank—Perform a blank analysis (baseline 9.5.2 Dilute the sample aliquot to approximately 2 mass %
blank) at least once per batch of samples. The blank analysis with the solvent.
may be without injection or by injection of an equivalent 9.5.3 Seal (cap) the vial, and mix the contents thoroughly to
solvent volume as used with sample injections, depending provide a homogeneous mixture.
upon the subsequent data handling capabilities for baseline/ 9.6 Sample Analysis—Using the analysis sequence protocol,
solvent compensation. The blank analysis is typically per- inject a sample aliquot into the gas chromatograph. Collect a
formed prior to sample analyses, but may be useful if deter- contiguous time slice record of the entire analysis (area slice
mined between samples or at the end of a sample sequence to mode).
provide additional data regarding instrument operation or 9.6.1 Be careful that the injection size chosen does not
residual sample carry-over from previous sample analyses. exceed the linear range of the detector. The typical sample size
9.3 Solvent Blank Run—Since not all of the material con- ranges from 0.2 to 2.0 µL of the diluted sample. The maximum
tained in fully formulated engine oil sample elute from the sample signal amplitude should not exceed the maximum
column, it is recommended that base oil samples without an calibration signal amplitude found in 9.4.1.

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 D6417 − 09

FIG. 1 Typical Calibration Curve with Plot

10. Calculation 10.4 Determine the percentage of engine oil volatilized to

10.1 Tabulate the RTs observed for the calibration standard 371°C, using Eq 3 as follows:
(n-paraffin blend) versus their respective boiling points. Cal- A 5 100 3 B/C (3)
culate the RT equivalent to 371°C (700°F), using linear
where:
regression and interpolation.
10.1.1 Descriptions of how to apply linear regression can be A = engine oil volatilized to 371°C, area %,
found in many mathematical textbooks. Scientific hand calcu- B = area of the engine oil up to 371°C,
C = area of total engine oil sample, and
lators and software programs may also be used to perform the
100 = factor to convert area/area to %.
calculations.
10.5 Report results as the area percent oil volatilized to
10.2 Subtract the blank analysis (see 9.3) from the sample
371°C (700°F) to the nearest 0.1 %. Fig. 3 shows typical report
analysis (see 9.6). If automatic baseline compensation (see
showing calculated volatility and chromatogram of a fully
Note 3) has been used, skip this step.
formulated engine oil.
10.3 Determine total sample area and area up to the reten-
tion time corresponding to 371°C (700°F). This may be done 11. Reference Materials
using either area slice summation or peak integration routines 11.1 The performance of this test method should be moni-
in commercial chromatography data systems. See Fig. 2 for tored by analyzing a reference material with each batch of
baseline definition of fully formulated engine oil sample. samples. The accepted value of the reference material shall be
10.3.1 If using area slice summation, use the calculation established by round robin testing. The precision of the value
procedure in Test Method D2887 to find start of sample elution established by the round robin testing shall meet the precision
and end of sample elution. statement in Section 12 of this test method. Suitable reference
[Link] Sum the area slices from start of sample elution to materials are available from a number of suppliers of standard
the last area slice found at the end of the run using a horizontal materials.
forward baseline. This is the total sample area, C.
[Link] Sum the area slices from start of sample to the slice 12. Precision and Bias4
corresponding to the RT corresponding to 371°C (700°F) found
12.1 Precision—The precision of this test method as deter-
in 10.1. This is the area of sample up to 371°C, B.
mined by the statistical examination of the interlaboratory test
10.3.2 If using peak integration software, set integration
data for results between 1.8 and 19.8 % is as follows (see Table
parameters to determine total sample area, C.
4):
[Link] Set integration parameters to determine the total
area from the start of sample elution to the RT corresponding
to 371°C found in 10.1, using a horizontal forward baseline. 4
Supporting data have been filed at ASTM International Headquarters and may
This is the area of sample up to 371°C, B . be obtained by requesting Research Report RR:D02-1451.

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 D6417 − 09

FIG. 2 Baseline Definition of Fully Formulated Engine Oil Sample

12.1.1 Repeatability—The difference between successive twenty.

0.5
test results obtained by the same operator with the same Reproducibility = 0.6036X
apparatus under constant operating conditions on identical test
material would, in the long run, in the normal and correct where:
operation of the test method, exceed the following values by X = volatility level
only one case in twenty. 12.2 Bias—No bias can be determined since the value for
Repeatability = 0.1352X 0.5
the percent volatilized at 371°C (700°F) is defined by the test
where: method.
X = volatility level
13. Keywords
12.1.2 Reproducibility—The difference between two single
and independent results obtained by different operators work- 13.1 boiling range distribution; engine oil, volatility; gas
ing in different laboratories on identical test material would, in chromatography; lubricants; petroleum; simulated distillation;
the long run, exceed the following values only one case in volatility

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 D6417 − 09

FIG. 3 Typical Report Showing Calculated Volatility and Chromatogram of a Fully Formulated Engine Oil

TABLE 3 Typical Calibration Report

Peak Retention Time Boiling Point (°F) Boiling Point (°C)
N-C5 0.14 97 36
N-C6 0.20 156 69
N-C7 0.32 209 98
N-C8 0.51 258 126
N-C9 0.90 303 151
N-C10 1.56 345 174
N-C11 2.48 385 196
N-C12 3.58 421 216
N-C13 4.73 456 235
N-C14 5.88 488 254
N-C15 7.00 519 271
N-C16 8.07 548 287
N-C17 9.11 576 302
N-C18 10.09 601 316
N-C20 11.92 651 344
N-C22 13.58 696 369
N-C24 15.12 736 391
N-C26 16.55 774 412
N-C28 17.89 808 431
N-C30 19.14 840 449
N-C32 20.32 870 466
N-C34 21.42 898 481
N-C36 22.47 925 496
N-C38 23.47 948 509
N-C40 24.41 972 522
N-C42 25.31 993 534
N-C44 26.17 1013 545
N-C46 26.99 1033 556
N-C48 27.78 1051 566
N-C50 28.54 1067 575
N-C52 29.27 1083 584
N-C54 29.97 1098 592
N-C56 30.64 1112 600
N-C58 31.28 1126 608
N-C60 31.91 1139 615
N-C62 32.5 1152 622

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 D6417 − 09
TABLE 4 Precision of Test Method D6417
Volatility
Repeatability Reproducibility
at 371°C (700°F), %
2.0 0.19 0.85
3.0 0.23 1.05
4.0 0.27 1.21
5.0 0.30 1.35
6.0 0.33 1.48
7.0 0.36 1.60
8.0 0.38 1.71
9.0 0.41 1.81
10.0 0.43 1.91
11.0 0.45 2.00
12.0 0.47 2.09
13.0 0.49 2.18
14.0 0.51 2.26
15.0 0.52 2.34
16.0 0.54 2.41
17.0 0.56 2.49
18.0 0.57 2.56
19.0 0.59 2.63

APPENDIX

(Nonmandatory Information)

X1. SUMMARY OF PAST CHANGES

X1.1 A list of changes made to the D6417–99 version to (3) Corrected Table 1, Footnote A.
create the D6417–02 revision follows: (4) Renamed Section 11 and reworded 11.1 to replace the
(1) Corrected selected Fahrenheit boiling point values in words “quality control materials” with “reference materials.”
Table 1 and added footnote explaining the derivation of the (5) Revised Table 3 to reflect changes made in correcting
corrected values. selected Fahrenheit boiling point values in Table 1.
(2) Expanded the quality control section of this test method
to include criterion for developing other suitable quality
control materials.

SUMMARY OF CHANGES

Subcommittee D02.04 has identified the location of selected changes to this standard since the last issue
(D6417–03) that may impact the use of this standard.

(1) Revised 1.4, Section 2, and 5.2 to remove all references to (2) Revised 2.2 and accompanying footnote and 5.2 to update
withdrawn Test Method D5480. the referenced Noack volatility method.

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