An American National Standard

Designation: D 5599 – 00

Standard Test Method for

Determination of Oxygenates in Gasoline by Gas
Chromatography and Oxygen Selective Flame Ionization
Detection1
This standard is issued under the fixed designation D 5599; 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 (e) indicates an editorial change since the last revision or reapproval.

1. Scope Products, and Lubricants3

1.1 This test method covers a gas chromatographic proce- D 4307 Practice for Preparation of Liquid Blends for Use as
dure for the quantitative determination of organic oxygenated Analytical Standards3
compounds in gasoline having a final boiling point not greater E 594 Practice for Testing Flame Ionization Detectors Used
than 220°C and oxygenates having a boiling point limit of in Gas or Supercritical Fluid Chromatography4
130°C. It is applicable when oxygenates are present in the 0.1 E 1064 Test Method for Water in Organic Liquids by
to 20 % by mass range. Coulometric Karl Fischer Titration5
1.2 This test method is intended to determine the mass E 1510 Practice for Installing Fused Silica Open Tubular
concentration of each oxygenate compound present in a gaso- Capillary Columns in Gas Chromatographs4
line. This requires knowledge of the identity of each oxygenate 3. Terminology
being determined (for calibration purposes). However, the
oxygen-selective detector used in this test method exhibits a 3.1 Definitions:
response that is proportional to the mass of oxygen. It is, 3.1.1 independent reference standards—calibration samples
therefore, possible to determine the mass concentration of of the oxygenates which are purchased or prepared from
oxygen contributed by any oxygenate compound in the sample, materials independent of the quality control check standards
whether or not it is identified. Total oxygen content in a and used for intralaboratory accuracy.
gasoline may be determined from the summation of the 3.1.2 oxygenate, n—an oxygen-containing compound, such
accurately determined individual oxygenated compounds. The as an alcohol or ether, which may be used as a fuel or fuel
summed area of other, uncalibrated or unknown oxygenated supplement. D 4175
compounds present, may be converted to a mass concentration 3.1.3 quality control check standards—calibration samples
of oxygen and summed with the oxygen concentration of the of the oxygenates for intralaboratory repeatability.
known oxygenated compounds. 4. Summary of Test Method
1.3 The values stated in SI units are to be regarded as the
standard. 4.1 An internal standard of a noninterfering oxygenate, for
1.4 This standard does not purport to address all of the example, 1,2-dimethoxyethane (ethylene glycol dimethyl
safety concerns, if any, associated with its use. It is the ether) is added in quantitative proportion to the gasoline
responsibility of the user of this standard to establish appro- sample. A representative aliquot of the sample and internal
priate safety and health practices and determine the applica- standard is injected into a gas chromatograph equipped with a
bility of regulatory limitations prior to use. capillary column operated to ensure separation of the oxygen-
ates. Hydrocarbons and oxygenates are eluted from the col-
2. Referenced Documents umn, but only oxygenates are detected with the oxygen-
2.1 ASTM Standards: selective flame ionization detector (OFID). A discussion of this
D 1744 Test Method for Water in Liquid Petroleum Prod- detector is presented in Section 6.
ucts by Karl Fischer Reagent2 4.2 Calibration mixtures are used for determining the reten-
D 4175 Terminology Relating to Petroleum, Petroleum tion times and relative mass response factors of the oxygenates
of interest. Suggested calibrant materials are listed in 8.2.
1
4.3 The peak area of each oxygenate in the gasoline is
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee measured relative to the peak area of the internal standard. A
D02.04.0L on Gas Chromatography.
Current edition approved Nov. 10, 2000. Published November 2000. Originally
published as D 5599 – 94. Last previous edition D 5599 – 95. 3
Annual Book of ASTM Standards, Vol 05.02.
2
Annual Book of ASTM Standards, Vol 05.01. 4
Annual Book of ASTM Standards, Vol 14.02.
5
Annual Book of ASTM Standards, Vol 15.05.

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

1
 D 5599 – 00
quadratic least-squares fit of the calibrated data of each 6.4 The methanizer consists either of a short porous layer
oxygenate is applied and the concentration of each oxygenate open tubular (PLOT) glass capillary tube internally coated with
calculated. aluminum oxide with adsorbed nickel catalyst or stainless steel
tubing containing a nickel-based catalyst. It is installed within
NOTE 1—While 1,2-dimethoxyethane has been found to be an appro-
priate internal standard, other oxygenates may be used provided they are or before the FID and is operated in the range from 350 to
not present in the sample and do not interfere with any compound of 450°C, depending on the instrument’s manufacturer.
interest.
NOTE 2—Gasolines with high sulfur content may cause a loss in
detector sensitivity thereby limiting the number of samples that can be
5. Significance and Use
analyzed before the catalyst needs replacement.
5.1 In gasoline blending, the determination of organic
oxygenated compounds is important. Alcohols, ethers, and 7. Apparatus
other oxygenates are added to gasoline to increase the octane 7.1 Gas Chromatograph—Any gas chromatograph can be
number and to reduce tailpipe emissions of carbon monoxide. used having the following performance characteristics:
They must be added in the proper concentration and ratios to 7.1.1 Column Temperature Programmer— The chromato-
meet regulatory limitations and to avoid phase separation and graph must be capable of reproducible linear temperature
problems with engine performance or efficiency. programming over a range sufficient for separation of the
5.2 This test method provides sufficient oxygen-to-hydro- components of interest.
carbon selectivity and sensitivity to allow determination of 7.1.2 Sample Introduction System—Any system capable of
oxygenates in gasoline samples without interference from the introducing a representative 0.1 to 1.0-µL liquid sample into
bulk hydrocarbon matrix. the split inlet device of the gas chromatograph. Microlitre
syringes, autosamplers, and liquid sampling valves have been
6. Theory of OFID Operation used successfully. The split injector should be capable of
6.1 The detection system selective for organic oxygen accurate split control in the range from 10:1 to 500:1.
consists of a cracking reactor, hydrogenating reactor (metha- 7.1.3 Carrier and Detector Gas Control— Constant flow
nizer), and a flame ionization detector (FID). The cracking control of carrier and detector gases is critical to optimum and
reactor, connected immediately after the gas chromatographic consistent analytical performance. Control is best provided by
capillary column, consists of a Pt/Rh capillary tube. Carbon the use of pressure regulators and fixed flow restrictors. The
monoxide (CO) is formed from compounds containing oxygen gas flow rates are measured by any appropriate means. The
according to the following reaction: supply pressure of the gas delivered to the gas chromatograph
CxHyOz → zCO 1 ~y/2!H 2 1 ~x 2 z!C (1) must be at least 70 kPa (10 psig) greater than the regulated gas
6.2 An excess layer of carbon is created in the Pt/Rh tube of at the instrument to compensate for the system back pressure.
the cracking reactor from the introduction of hydrocarbons In general, a supply pressure of 550 kPa (80 psig) will be
from the sample or, if so designed, from a hydrocarbon (for satisfactory.
example, pentane or hexane) doping system, or both. This layer 7.2 OFID Detector System, consisting of a cracking reactor,
of carbon facilitates the cracking reaction and suppresses methanizer, and FID. A schematic of a typical OFID system is
hydrocarbon response. shown in Fig. 1.
6.3 The carbon monoxide formed in the cracking reactor is 7.2.1 The detector must meet or exceed the typical specifi-
converted to methane in the hydrogenating reactor according to cations given in Table 1 of Practice E 594 while operating in
the following reaction: the normal FID mode as specified by the manufacturer.
7.2.2 In the OFID mode, the detector shall meet or exceed
CO 1 3H 2 → CH4 1 H2O (2) the following specifications: (a) equal to or greater than 103
The CH4 is subsequently detected with an FID. linearity, (b) less than 100-ppm mass oxygen (1-ng O/s)

FIG. 1 Schematic of an OFID

2
 D 5599 – 00
sensitivity, (c) greater than 106 selectivity for oxygen com- depending on the instrument’s manufacturer. (Warning—
pounds over hydrocarbons, (d) no interference from coeluting Helium and nitrogen are compressed gases under high pres-
compounds when 0.1 to 1.0-µL sample is injected, (e) equimo- sure.)
lar response for oxygen. 8.5.4 Additional purification of the carrier, air, and hydro-
7.3 Column—A 60-m by 0.25-mm inside diameter fused gen is recommended. Use molecular sieves, Drierite, charcoal,
silica open tubular column containing a 1.0-µm film thickness or other suitable agents to remove water, oxygen, and hydro-
of bonded methyl silicone liquid phase is used. Equivalent carbons from the gases.
columns which provide separation of all oxygenates of interest 8.6 Sample Container—Glass vials with crimp on or screw-
may be used. down sealing caps with self-sealing polytetrafluoroethylene
7.4 Integrator—Use of an electronic integrating device or (PTFE)–faced rubber membranes are used to prepare calibra-
computer is required. The device and software should have the tion standards and samples for analyses.
following capabilities:
9. Preparation of Apparatus
7.4.1 Graphic presentation of the chromatogram,
7.4.2 Digital display of chromatographic peak areas, 9.1 Chromatograph and OFID—Place instrument and de-
7.4.3 Identification of peaks by retention time, tector into operation in accordance with the manufacturer’s
7.4.4 Calculation and use of response factors, and instructions. Install the capillary column according to Practice
7.4.5 Internal standard calculation and data presentation. E 1510. Adjust the operating conditions to provide for separa-
tion of all oxygenates of interest. Typical conditions used with
8. Reagents and Materials the column specified in 7.3 are listed in Table 1.
8.1 Purity of Reagents—Reagents grade chemicals shall be 9.2 System Performance—At the beginning of each day of
used in all tests. Unless otherwise indicated, it is intended that operation, inject an oxygenate-free gasoline sample into the
all reagents shall conform to the specifications of the Commit- chromatograph to ensure minimum hydrocarbon response. If
tee on Analytical Reagents of the American Chemical Society, hydrocarbon response is detected, the OFID is not operating
where such specifications are available.6 Other grades may be effectively and must be optimized according to the manufac-
used, provided it is first ascertained that the reagent is of turer’s instructions before the sample can be analyzed.
sufficiently high purity to permit its use without lessening the 10. Calibration and Standardization
accuracy of the determination. 10.1 Retention Time Identification— Determine the reten-
8.2 Calibrant Materials—The following compounds may tion time of each oxygenate component by injecting small
be used for calibrating the detector: methanol, ethanol, amounts either separately or in known mixtures. Table 2 gives
n-propanol, iso-propanol, n-butanol, tert-butanol, sec-butanol, typical retention times for the oxygenates eluting from a 60-m
iso-butanol, tert-pentanol, methyl tert-butylether (MTBE), methyl silicone column temperature programmed according to
tert-amylmethylether (TAME), ethyl tert-butylether (ETBE), conditions given in Table 1. A chromatogram of a blend of
di-iso-propylether (DIPE). (Warning—These materials are oxygenates is given in Fig. 2.
very flammable and may be harmful or fatal when ingested, 10.2 Preparation of Calibration Samples— The calibration
inhaled, or allowed to be absorbed through the skin.) samples are prepared gravimetrically in accordance with Prac-
8.3 Internal Standard—Use one of the compounds listed in tice D 4307 by blending known weights of organic oxygenate
8.2 that is not present in the sample. If all of the materials in 8.2 compounds (such as listed in 8.2) with a known weight internal
are likely to be present in the test sample, use another organic standard and diluting to a known weight with an oxygenate-
oxygenate of high-grade purity that is separated from all other free gasoline. The calibration samples should contain the same
oxygenates present (for example, 1,2-dimethoxyethane).
8.4 Dopant—If the OFID is so designed, reagent-grade TABLE 1 Typical Operating Conditions
pentane is used as a hydrocarbon dopant for the cracking Temperatures, °C
reactor. (Warning—Pentane is extremely flammable and Injector 250
harmful when inhaled.) Column 50°C (hold 10 min), ramp 8°/min to 250°C
Detector Methanizer 350–450
8.5 Instrument Gases—The gases supplied to the gas chro- Reactor 850–1300
matograph and detector are:
Flows, mL/min
8.5.1 Air, zero grade. (Warning—Compressed air is a gas
Column carrier gas 1
under high pressure and supports combustion.) Detector gases Air: 300
8.5.2 Hydrogen, pure grade, 99.9 mol %. ( Warning— H2:30
Hydrogen is an extremely flammable gas under high pressure.) Auxiliary (for dopant, if available) H2: 0.6
8.5.3 Helium or nitrogen as column carrier gas, 99.995 mol Sample Size 0.1–1.0 µLA
% minimum purity, or a blend of 95 % helium/5 % hydrogen, Split Ratio 100–1
A
Sample size and split ratio must be adjusted so that the oxygenates in the
range from 0.1 to 20.0 mass % are eluted from the column and measured linearly
6
at the detector. Each laboratory must establish and monitor the conditions that are
Reagent Chemicals, American Chemical Society Specifications, American needed to maintain linearity with their individual instruments. Nonlinearity is most
Chemical Society, Washington, DC. For suggestions on the testing of reagents not commonly observed when using an OFID with samples containing high levels of
listed by the American Chemical Society, see Analar Standards for Laboratory individual oxygenates and can be compensated for by either decreasing the
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia sample size, increasing the split ratio, or diluting the sample with an oxygenate-
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, free gasoline. A sample size of 0.5 µL and a split ratio of 100:1 has been used
MD. successfully in most cases.

3
 D 5599 – 00
TABLE 2 Oxygenates Retention Times, Relative Response to the nearest 0.1 mg. Repeat this process for any additional
Factors, and Molecular Masses (Conditions as in Table 1) oxygenates of interest except the internal standard. Add
Relative Relative oxygenate-free gasoline to dilute the oxygenates to the desired
Retention Molecular
Compound Response Response
Time min Mass
Factors A,B
FactorsB,C,D
concentration. Record the mass of gasoline added to the nearest
0.1 mg, and determine and label the standard according to the
Dissolved Oxygen 5.33 32.0 D D
Water 5.89 18.0 D D mass % quantities of each oxygenate added. These standards
Methanol 6.45 32.0 0.70 0.98 are not to exceed 20 mass % for any individual pure component
Ethanol 7.71 46.1 0.99 0.97
Isopropanol 8.97 60.1 1.28 0.96
due to potential hydrocarbon breakthrough or loss, or both, of
tert-Butanol 10.19 74.1 1.63 0.99 calibration linearity. To minimize evaporation of light compo-
n-Propanol 11.76 60.1 1.30 0.98 nents, chill all chemicals and gasoline used to make standards.
MTBE 12.73 88.2 1.90 0.97
sec-Butanol 13.92 74.1 1.59 0.97
10.2.2 Tare the glass sample container, a PTFE-faced rubber
DIPE 14.53 102.2 2.26 1.00 septum sealing cap, and contents prepared in 10.2.1. Add a
Isobutanol 15.32 74.1 1.64 0.99 quantity of an internal standard (such as 1,2–dimethoxyethane)
ETBE 15.49 102.2 2.25 0.99
tert-Pentanol 15.97 88.1 2.03 1.04
and record its mass to the nearest 0.1 mg. The mass of the
1,2-dimethoxyethane 16.57 90.1 1.00 1.00 internal standard should be between 2 and 6 % of the mass of
n-Butanol 17.07 74.1 1.69 1.03 the calibration sample.
TAME 18.23 102.2 2.26 1.00
10.2.3 Ensure that the prepared standard is thoroughly
A
Based on mass percent oxygenate compound basis.
B
Relative to 1,2-dimethoxyethane.
mixed, and transfer approximately 2 mL of the solution to a
C
Based on mass percent oxygen basis. vial compatible with the autosampler if such equipment is
D
Not determined. used.
10.2.4 At least five concentrations of each of the expected
oxygenates should be prepared. The standards should be as
equally spaced as possible within the range and may contain
more than one oxygenate. A blank for zero concentration
assessment shall also be included. Additional standards should
be prepared for other oxygenates of concern.
NOTE 3—If carryover is suspected to possibly occur, the blank should
be run following a calibration sample containing high levels of oxygen-
ates.
10.3 Standardization—Run the calibration samples and es-
tablish a calibration curve by performing a least-squares fit of
the response ratios of the oxygenate standards to their amount
ratios, as follows.
10.3.1 Calculate the response ratio ( rsps):
rsps 5 ~A s/Ai! (3)

where:
As = peak area of the test oxygen compound in the cali-
bration sample, and
Ai = peak area of the internal standard in the calibration
sample,
and the amount ratio (amts):
NOTE 1—Operating conditions in accordance with Table 1. amts 5 ~Ws/Wi! (4)
FIG. 2 Chromatogram of an Oxygenates Blend
where:
oxygenates (in similar concentrations) as are expected in the Ws = mass of the test oxygen compound in the calibration
sample under test. Before preparing the standards, determine sample, g, and
Wi = mass of the internal standard in the calibration
the purity of the oxygenate stocks and make corrections for the
sample, g,
impurities found. Whenever possible, use stocks of at least
99.9 % purity. Correct for the purity of the components for for each level of each oxygenate, s.
water content determined by Test Method D 1744 or Test 10.3.2 For each oxygenate, s, calibration set, obtain the
Method E 1064. Quality control check standards may be quadratic least-squares fit equation in the following form
prepared from the same oxygenate stocks and by the same (forced through the origin):
analyst. Quality control check standards must be prepared from rsp s 5 ~bo!~amts! 1 b l ~amts!2 (5)
separate batches of the final diluted standards.
10.2.1 Tare a glass sample container and its PTFE-faced where:
rubber septum sealing cap. Transfer a quantity of an oxygenate rsps = response ratio for oxygenate s (y-axis),
bo = linear regression coefficient for oxygenate s,
to the sample container and record the mass of the oxygenate

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 D 5599 – 00

amts = amount ratio for oxygenate s (x-axis), and ate’s response ratio (rsp s) and the coefficient of its quadratic
bl = quadratic regression coefficient. calibration curve into Eq 5 (10.3.1) and solving.
10.3.3 Fig. 3 gives an example of a quadratic least-squares 12.1.3 Apply Eq 6 to determine the mass % of each
fit for MTBE and the resulting equation in the form of Eq 5. calibrated oxygenate.
Check the correlation r2 value for each oxygenate calibration. ~amts!~Wi!~100 %!
The r2 value should be at least 0.99 or better. ws 5 Wg (6)

11. Procedure where:

11.1 Keep samples refrigerated until ready for analysis. ws = mass % of oxygenate in gasoline sample,
Bring samples to room temperature prior to analysis. amts = amount ratio of oxygenate as determined in 12.1.2,
11.2 Tare the sample container and its rubber-faced PTFE- Wi = mass of internal standard added to gasoline sample,
faced sealing cap. Transfer 1 to 10 g of the sample to the g, and
container and seal immediately. Weigh the sample container Wg = mass of gasoline sample, g.
and contents to the nearest 0.1 mg and record the mass of test 12.1.4 If the mass % of any oxygenate exceeds its calibrated
sample. range, gravimetrically dilute a portion of the original sample
11.3 Tare the sample container and contents, then inject with oxygenate-free gasoline to a concentration within the
through the rubber membrane a volume of the same internal calibrated range and analyze the diluted sample in accordance
standard used in generating the standards. Record the mass of with Section 11 and 12.1. Correct all mass % oxygenate values
internal standard added to the nearest 0.1 mg. The mass of by multiplying by the dilution factor.
internal standard should be 2 to 6 % of the test sample but not 12.2 Calculate the total MTBE-equivalent mass % of uncali-
less than 50 mg. brated oxygenates as follows:
11.4 Ensure that the sample (gasoline plus internal standard) 12.2.1 Sum the peak areas of the uncalibrated oxygenates
is thoroughly mixed. Transfer an aliquot of the solution to a that are present. Do not include the peak areas due to dissolved
vial compatible with the autosampler if such equipment is oxygen, water, and the internal standard. Calculate the re-
used. Seal the vial with a PTFE-lined septum cap. sponse ratio (rsps) for the summed areas of the uncalibrated
11.5 Inject a suitable quantity (0.1 to 1.0 µL) of the sample oxygenates using Eq 3 (10.3.1).
containing internal standard into the chromatograph using the 12.2.2 Calculate the amount ratio ( amts) for the uncali-
same technique and sample size as used for the calibration brated oxygenates in the gasoline sample by substituting the
standards. The test portion size should be such as not to exceed response ratio (determined in 12.2.1) and the coefficients of the
the capacity of the column or linearity of the detector. MTBE calibration curve into Eq 5 (10.3.1) and solving.
11.6 Acquire peak area and retention time data by way of 12.2.3 Apply Eq 6 (12.1.3) to determine the total MTBE-
electronic integrator or computer and, if desired, also by chart equivalent mass % of the uncalibrated oxygenates.
recorder. 12.3 Calculate the total mass % oxygen in the gasoline
12. Calculation and Report sample as follows:
12.1 Calculate the mass % of each calibrated oxygenate as 12.3.1 Convert the mass % oxygenate of each individual,
follows: calibrated oxygenate to mass % oxygen and sum according to
12.1.1 After identifying the various oxygenates by retention the following equation:
times, obtain the areas of all calibrated oxygenate peaks and @~ws!~16.0!~Ns!#
Ocal 5 ( (7)
that of the internal standard. Calculate the area response ratio Ms
(rsp s) for each of the oxygenates using Eq 3 (10.3.1). or
12.1.2 Calculate the amount ratio ( amts) for each calibrated
oxygenate in the gasoline sample, by substituting that oxygen- @w1#@16.0#@N1# @w2#@16.0#@N2#
Ocal 5 M1 1 M2 1... (8)

where:
Ocal = total mass percent oxygen from the calibrated
oxygenates,
ws = mass % of each oxygenate as determined using Eq
6,
Ns = number of oxygen atoms in the oxygenate mol-
ecule,
M s = molecular mass of the oxygenate as given in Table
2, and
16.0 = atomic mass of oxygen.
12.3.2 Convert the total MTBE-equivalent mass % of un-
calibrated oxygenates to mass % oxygen according to the
following equation:
~wsu!~16.0!~Ns!
Ouncal 5 Ms (9)
FIG. 3 An Example of a Quadratic Least-Squares Fit for MTBE

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 D 5599 – 00
TABLE 3 Precision Interval as Determined from Cooperative Study Data Repeatability
Component Repeatability
Wt %
Total
MeOH EtOH iPA tBA nPA MTBE sBA DIPE iBA ETBE tAA nBA TAME
Oxygen
0.20 0.03 0.01 0.02 0.02 0.02 0.02 0.01 0.02 0.01 0.01 0.03 0.03 0.02 ...
0.50 0.05 0.02 0.03 0.03 0.03 0.03 0.02 0.03 0.02 0.01 0.04 0.04 0.03 ...
1.00 0.07 0.03 0.04 0.05 0.04 0.05 0.03 0.05 0.03 0.04 0.05 0.06 0.04 0.03
2.00 0.10 0.06 0.06 0.08 0.05 0.07 0.04 0.08 0.05 0.07 0.07 0.08 0.06 0.06
3.00 0.12 0.08 0.07 0.10 0.06 0.09 0.05 0.10 0.07 0.10 0.08 0.10 0.08 0.08
4.00 0.13 0.11 0.08 0.12 0.06 0.11 0.06 0.12 0.09 0.13 0.09 0.11 0.09 0.11
5.00 0.15 0.13 0.09 0.14 0.07 0.13 0.07 0.14 0.11 0.16 0.10 0.13 0.10 0.13
6.00 0.17 0.16 0.10 0.16 0.07 0.14 0.08 0.16 0.12 0.19 0.10 0.14 0.11 ...
10.00 0.22 0.25 0.14 0.22 0.09 0.19 0.10 0.22 0.18 0.29 0.13 0.17 0.15 ...
12.00 0.24 0.29 0.15 0.25 0.09 0.21 0.11 0.25 0.21 0.34 0.14 0.19 0.17 ...
14.00 ... ... ... ... ... 0.23 ... 0.28 ... 0.39 ... ... 0.18 ...
16.00 ... ... ... ... ... 0.25 ... 0.30 ... 0.43 ... ... 0.20 ...
20.00 ... ... ... ... ... 0.28 ... 0.35 ... 0.53 ... ... 0.23 ...
Reproducibility
Component
Wt % Total
MeOH EtOH iPA tBA nPA MTBE sBA DIPE iBA ETBE tAA nBA TAME
Oxygen
0.20 0.06 0.07 0.06 0.05 0.04 0.02 0.05 0.05 0.05 0.07 0.07 0.14 0.08 ...
0.50 0.14 0.16 0.13 0.11 0.09 0.05 0.10 0.10 0.11 0.14 0.12 0.18 0.15 ...
1.00 0.25 0.27 0.21 0.20 0.17 0.10 0.17 0.16 0.19 0.25 0.18 0.22 0.24 0.13
2.00 0.45 0.47 0.35 0.28 0.31 0.19 0.28 0.26 0.34 0.43 0.26 0.27 0.39 0.23
3.00 0.64 0.65 0.47 0.48 0.45 0.28 0.38 0.35 0.47 0.60 0.33 0.31 0.51 0.32
4.00 0.82 0.82 0.59 0.61 0.58 0.37 0.47 0.43 0.60 0.75 0.39 0.33 0.62 0.41
5.00 1.00 0.98 0.69 0.72 0.70 0.46 0.55 0.50 0.72 0.89 0.44 0.36 0.73 0.49
6.00 1.17 1.13 0.79 0.84 0.82 0.55 0.63 0.57 0.84 1.03 0.48 0.38 0.83 ...
10.00 1.81 1.70 1.15 1.26 1.29 0.89 0.91 0.82 1.28 1.54 0.64 0.44 1.17 ...
12.00 2.12 1.97 1.32 1.46 1.51 1.06 1.04 0.93 1.49 1.78 0.71 0.46 1.33 ...
14.00 ... ... ... ... ... 1.23 ... 1.04 ... 2.01 ... ... 1.48 ...
16.00 ... ... ... ... ... 1.39 ... 1.15 ... 2.23 ... ... 1.63 ...
20.00 ... ... ... ... ... 1.72 ... 1.34 ... 2.66 ... ... 1.90 ...

where: Oxygenate Concentration, Upper Limit for Range, mass %

Ouncal = total mass % oxygen from the uncalibrated oxy- mass %

genates, Methanol 0.20 to 1.00 0.010 + 0.043C

Wsu = MTBE-equivalent mass % of uncalibrated oxy- Methanol 1.00 to 12.00 0.053C
genates, Ethanol 1.00 to 12.00 0.053C
MTBE 0.20 to 20.00 0.069 + 0.029C
Ns = number or oxygen atoms in MTBE molecule, DIPE 1.00 to 20.00 0.048C
Ms = molecular mass of MTBE as given in Table 2, and ETBE 1.00 to 20.00 0.074C
16.0 = atomic mass of oxygen. TAME 1.00 to 20.00 0.060C
12.3.3 Calculate the total mass % oxygen in the gasoline
where:
sample by summing the contributions from the calibrated C = ~Co 1 Cd!/2
components and the uncalibrated components. R = ?Co 2 C d?
Otot 5 Ocal 1 Ouncal (10) Co = concentration of the original sample, and
12.4 Report the mass % oxygenate of each calibrated Cd = concentration of the duplicate sample.
oxygenate to the nearest 0.01 %. Also report the total mass % 13.1.2 If these limits are exceeded, the sources of error in
oxygen in the gasoline sample to the nearest 0.1 %. the analysis should be determined, corrected, and all analyses
subsequent to and including the last duplicate analysis con-
13. Quality Control Checks firmed to be within the compliance specifications should be
13.1 Routinely monitor the intralaboratory repeatability and repeated.
accuracy of the analysis as follows: 13.2 Intralaboratory Accuracy:
13.1.1 Intralaboratory Repeatability: 13.2.1 If the measured concentration of a quality control
13.1.1.1 Quality control check standards may be prepared check standard is outside the range of 100.0 6 6.0 % of the
from the same oxygenate stocks prepared in 10.2 and covering theoretical concentration for a selected oxygenate of 1.0 mass
the range given in 13.1.1.4. % or above, the sources of error in the analysis should be
13.1.1.2 Prepare and analyze duplicates of the quality con- determined, corrected, and all analyses subsequent to and
trol check standards at a rate of one per analysis batch or at including the last standard analysis confirmed to be within the
least one per ten samples, whichever is more frequent. compliance specifications should be repeated.
13.1.1.3 Duplicates should be carried through all sample 13.2.2 Independent reference standards may be purchased
preparation steps independently. or prepared from materials that are independent of the quality
13.1.1.4 The range (R) for duplicate samples should be less control standards and should not be prepared by the same
than the following limits: analyst. For the specification limits listed in 13.2.2.2, the

6
 D 5599 – 00
concentration of the reference standards should be in the range Methanol (MeOH) 0.07 (X0.49)A
given in 13.1.1.4. Ethanol (EtOH) 0.03 (X0.92)
Iso-propanol (iPA) 0.04 (X0.54)
13.2.2.1 Independent reference standards should be ana- tert-Butanol (tBA) 0.05 (X0.65)
lyzed at a rate of one per analysis batch or at least one per 100 n-Propanol (nPA) 0.04 (X0.35)
samples, whichever is more frequent. MTBE 0.05 (X0.58)
sec-Butanol (sBA) 0.03 (X0.54)
13.2.2.2 If the measured concentration of an independent DIPE 0.05 (X0.65)
reference standard is outside the range of 100.0 6 10.0 % of Iso-butanol (iBA) 0.03 (X0.79)
the theoretical concentration for a selected oxygenate of 1.0 ETBE 0.04 (X0.86)
tert-Pentanol (tAA) 0.05 (X0.41)
mass % or above, the sources of error in the analysis should be n-Butanol (nBA) 0.06 (X0.46)
determined, corrected, and all analyses subsequent to and TAME 0.04 (X0.58)
including the last independent reference standard analysis Total Oxygen 0.03 (X0.93)
A
confirmed to be within the compliance specifications in that X is the mean mass % of the component.
batch should be repeated. 14.1.2 Reproducibility—The difference between two single
13.3 Control charts may be utilized to monitor the variabil- and independent results obtained by different operators work-
ity of measurements from the quality control check standards ing in different laboratories on identical material would, in the
and independent reference standards in order to optimally long run, exceed the following values in only one case in
detect abnormal situations and ensure a stable measurement twenty (see Table 3).
process. Reproducibility in Oxygenates in Gasolines
Component Reproducibility
Methanol (MeOH) 0.25 (X0.86)
14. Precision and Bias 7 Ethanol (EtOH) 0.27 (X0.80)
14.1 Data obtained from a 10-laboratory round robin on the Iso-propanol (iPA) 0.21 (X0.71)
tert-Butanol (tBA) 0.20 (X0.80)
measurement of 13 oxygenates and total oxygen in 12 gasoline n-Propanol (nPA) 0.17 (X0.88)
samples were examined. The precision of this test method as MTBE 0.10 (X0.95)
determined by a statistical examination of the interlaboratory sec-Butanol (sBA) 0.17 (X0.73)
DIPE 0.16 (X0.71)
test results based on 1,2-dimethoxyethane as the internal Iso-butanol (iBA) 0.19 (X0.83)
standard is as follows: ETBE 0.25 (X0.79)
14.1.1 Repeatability—The difference between successive tert-Pentanol (tAA) 0.18 (X0.55)
n-Butanol (nBA) 0.22 (X0.30)
results obtained by the same operator with the same apparatus TAME 0.24 (X0.69)
under constant operating conditions on identical test materials Total Oxygen 0.13 (X0.83)
would, in the long run and in the normal and correct operation
14.2 Bias—A statement of bias is currently being developed
of the test method, exceed the following values only one case
by the responsible study group.
in twenty (see Table 3).
Repeatability for Oxygenates in Gasoline 15. Keywords
Component Repeatability
15.1 alcohols; DIPE (Di-iso-propylether); ETBE (ethyl tert-
butylether); ethanol; gas chromatography; gasoline; methanol;
7
Supporting data are available from ASTM Headquarters. Request RR:D02- MTBE (methyl tert-butylether); oxygenates; oxygen-selective
1359. detection; TAME (tert-amylmethylether)

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