Designation: D7920 − 15´1

Standard Test Method for

Determination of Fuel Methanol (M99) and Methanol Fuel
Blends (M10 to M99) by Gas Chromatography1
This standard is issued under the fixed designation D7920; 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.

ε1 NOTE—Section 16 was corrected editorially in September 2015.

1. Scope D4175 Terminology Relating to Petroleum, Petroleum

1.1 This test method covers the determination of the metha- Products, and Lubricants
nol content, by gas chromatography, of M10 to M99 in D4307 Practice for Preparation of Liquid Blends for Use as
methanol fuel blends, including fuel methanol (M99). Analytical Standards
1.1.1 Methanol may be determined from 10 % to 99 % by D4814 Specification for Automotive Spark-Ignition Engine
volume. Fuel
D4626 Practice for Calculation of Gas Chromatographic
1.2 This test method is designed to measure not only
Response Factors
methanol in the blended gasoline but also the impurities in fuel
methanol (M99) itself in the range of 5 mg/kg to 1000 mg/kg. D5797 Specification for Fuel Methanol (M70-M85) for Au-
However, not all impurities are measured nor detected by this tomotive Spark-Ignition Engines
test method. D6299 Practice for Applying Statistical Quality Assurance
1.2.1 Water cannot be determined by this test method and and Control Charting Techniques to Evaluate Analytical
shall be measured by a procedure such as Test Method D1364 Measurement System Performance
and the result used to correct the concentrations determined by E29 Practice for Using Significant Digits in Test Data to
this test method. Determine Conformance with Specifications
E355 Practice for Gas Chromatography Terms and Relation-
1.3 The values stated in SI units are to be regarded as
ships
standard. No other units of measurement are included in this
E594 Practice for Testing Flame Ionization Detectors Used
standard.
in Gas or Supercritical Fluid Chromatography
1.4 This standard does not purport to address all of the E1064 Test Method for Water in Organic Liquids by Coulo-
safety concerns, if any, associated with its use. It is the metric Karl Fischer Titration
responsibility of the user of this standard to establish appro- E1510 Practice for Installing Fused Silica Open Tubular
priate safety and health practices and determine the applica-
Capillary Columns in Gas Chromatographs
bility of regulatory limitations prior to use.
3. Terminology
2. Referenced Documents
2.1 ASTM Standards:2 3.1 This test method makes reference to many common
D1364 Test Method for Water in Volatile Solvents (Karl chromatographic procedures, terms, and relationships. Detailed
Fischer Reagent Titration Method) definitions can be found in Terminology D4175 and Practices
D4057 Practice for Manual Sampling of Petroleum and D4626, E355, and E594.
Petroleum Products 3.2 Definitions:
3.2.1 analyte, n—a specific compound to be measured
quantitatively in a mixture of compounds.
1
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of 3.2.2 analytical column, n—a chromatographic column used
Subcommittee D02.04.0L on Gas Chromatography Methods. to further separate a specific analyte from a mixture of
Current edition approved Aug. 1, 2015. Published September 2015. DOI:
10.1520/D7920-15E01.
compounds which can coelute in the primary column.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or 3.2.3 analytical detector, n—a device used to quantify the
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on compounds of interest after they elute from the analytical
the ASTM website. column.

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

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 D7920 − 15´1
3.2.4 fuel methanol (M99), n—methyl alcohol produced for to transfer the methanol from the primary column to the
the purpose of blending with gasoline to make a fuel for analytical column. A further separation takes place in the
spark-ignition internal combustion engines. analytical polar column suitable for the polarity of methanol.
3.2.4.1 Discussion—Fuel methanol is typically produced After elution from the secondary column, the methanol is
with 99 % by volume methyl alcohol. analyzed by the analytical detector. Fuel methanol (M99) is
3.2.5 gasoline, n—a volatile mixture of liquid analyzed by the primary column only without the execution of
hydrocarbons, generally containing small amounts of a heart-cut. Analysis is made in the monitor detector. In the
additives, suitable for use as a fuel in spark-ignition internal case of fuel methanol (M99) the mass percent is determined by
combustion engines. D4814 difference.
3.2.6 heart-cut, n—in gas chromatography, a procedure in 5. Significance and Use
which the analyte in question is transferred from one column to
5.1 Methanol is used in blends with gasoline at levels of
a different column, usually of the opposite polarity.
70 % to 85 % by volume, as specified in Specification D5797.
3.2.7 internal standard (IS), n—a high purity compound not This test method provides a quantitative approach to measure
present in the sample which is added to the sample and used to the methanol content in methanol fuel blends, from 10 % to
calculate quantitatively the component of interest. 99 % by volume. The usual concentration is 70 % to 85 % by
3.2.7.1 Discussion—The internal standard is added in a volume (M70 to M85). The method is also used to analyze fuel
constant amount to all calibration standards, see 7.4.2.1. methanol (M99) prior to blending.
3.2.8 mass response factor (MRF), n—a constant of propor-
tionality that converts area percent to mass percent. 6. Apparatus
3.2.9 methanol, n—methyl alcohol, the chemical compound 6.1 Gas Chromatograph, capable of operating at the condi-
CH3OH. tions listed in Table 1 and Table 2. A heated flash vaporizing
inlet, also known as a split inlet, is designed to provide a linear
3.2.10 methanol fuel blend, n—a fuel consisting primarily of
sample split injection (for example, 500:1). This inlet is
a mixture of methanol with gasoline.
required for proper sample introduction. Carrier gas controls
3.2.10.1 Discussion—Typically methanol fuel blends are
shall be of adequate precision to provide reproducible column
70 % to 85 % by volume, identified as M70 to M85.
flows and split ratios in order to maintain analytical integrity.
3.2.11 microfluidic device, n—a chromatographic switching Pressure and flow control devices used shall be designed to
valve constructed with micro channels, usually having five attain the linear velocity required for optimum operation of the
ports and to which the columns, restrictors and auxiliary columns. Two separate flame ionization detectors are required
pressure devices are connected in order to carry out a heart-cut. for this test method. The use of one detector alone is not
3.2.11.1 Discussion—An auxiliary carrier gas is fed to the possible as the setting of the heart-cut times will be difficult
device which has two ports of entry such that switching the and the reliability of the exact cut time determination may be
carrier gas from one port to the other results in changing the compromised. Detectors should meet the sensitivity criteria of
direction of the flow of the primary column to either a restrictor Practice E594.
or to the analytical column. 6.1.1 A heart-cut is a technique which utilizes a switching
3.2.12 monitor detector, n—a device used to measure the device to which the following five (5) components are con-
elution of the analyte from the primary column. nected: (1) a primary column, usually non-polar which spans
3.2.12.1 Discussion—The monitor detector is used to deter- from the inlet to the device, (2) an analytical column, usually
mine the heart-cut time (see 6.1.1), that is, the time where the
peak of interest begins and where the peak of interest ends. TABLE 1 Conditions for Analysis of Methanol Fuel Blend—
3.2.13 MXX, n—an abbreviation that represents a fuel con- Carrier Helium
sisting primarily of methanol (methyl alcohol) and hydrocar- Valve ON interval, min 2.37–2.60 3.25–3.36
Inlet temperature, °C 250
bons in which ‘XX’ is the percent by volume of methanol in the Split ratio 500/1
blended fuel. Primary column pressure, kPa 259.2
Primary column flow, mL/min 2
3.2.14 primary column, n—in chromatography, a device Analytical column pressure, kPa 190.1
used to perform a primary separation of a mixture of com- Analytical column, flow, mL/min 3
pounds. Oven, initial T °C 50
Initial hold time, min 5.5
3.2.14.1 Discussion—The primary column, also known as a Oven temperature rate, °C /min 15
monitor column, is used to separate the analyte of interest and Final oven temperature, °C 190
to determine the start time and the end time of the heart-cut. Final hold time, min 3
Analytical FID, T °C 300
Hydrogen, mL/min 45
4. Summary of Test Method Air, mL/min 450
Make up, N2 mL/min 25
4.1 The sample is injected in to the gas chromatograph Monitor, FID, T °C 300
where components are separated in the primary column and Hydrogen, mL/min 45
subsequently are eluted through the restrictor and detected by Air, mL/min 450
Make up, N2 mL/min 25
the monitor detector. The methanol is identified and the Volume injected, µL 0.2
heart-cut window is determined. The instrument settings are set

2
 D7920 − 15´1
TABLE 2 Conditions for Analysis of Methanol Fuel Blend— 6.3.3 A balance restrictor is required; composed of inert
Carrier Hydrogen deactivated fused silica whose dimensions provide the same
Valve ON interval, min 1.42-1.52 1.94–2.06 flow resistance as that of the analytical column while minimiz-
Inlet temperature, °C 250
Split ratio 500/1
ing the holdup time of peaks eluting from the primary column
Primary column pressure, kPa 172.6 to the monitor detector. A typical sized restrictor will be of
Primary column flow, mL/min 2.5 approximately 1 m in length and 0.1 mm internal diameter. It
Analytical column pressure, kPa 120.7
Analytical column, flow, mL/min 3.5 is connected from the device to the monitor detector. This
Oven, initial T °C 50 length is sufficient to accommodate the equivalent pneumatic
Initial hold time, min 5.5 resistance of the analytical column. The dimensions of the
Oven temperature rate, °C /min 15
Final oven temperature, °C 190 restrictor facilitate the fast transfer of the eluents from the
Final hold time, min 3 primary column so as to provide negligible delay in reaching
Analytical FID, T °C 300 the monitor detector. Thus accurate cut times can be deter-
Hydrogen, mL/min 45
Air, mL/min 450 mined.
Make up, N2 mL/min 25
Monitor, FID, T °C 300
6.4 Microfluidic Device—The microfluidic device shall be
Hydrogen, mL/min 45 treated to become inert in order to avoid adsorption of any
Air, mL/min 450 components in the sample. It shall be manufactured with
Make up, N2 mL/min 25
Volume injected, µL 0.2
extremely small volumes and grooves so as not to introduce
peak broadening or dead volumes. These devices are available
from several manufacturers.
6.5 Electronic Pressure Control—An electronic means of
controlling the auxiliary pressure is required to cause the
a polar column, that spans from the device to the analytical
transfer of the components from the primary column to the
detector, (3) a restrictor or a tubing of small diameter which
analytical column. This controller is connected to the micro-
connects from the device to a second detector whose function
fluidic device through a solenoid. The pressure controller must
is to serve as the monitor detector, (4) an external pressure
be capable of controlling pressures to within at least 0.069 kPa.
device which controls the pressure at the point where the two
columns coincide, and finally, (5), a solenoid that directs the 6.6 Solenoid—Device required to switch the direction of the
pressure to the two points of the device. By switching the flow from the restrictor point to the analytical column point.
applied pressure, the components eluting from the primary Typical solenoids should be capable of executing more than
column can either be sent to the monitor detector or to the one million cycles. The solenoid should be free of components
analytical column where further separation occurs and thus the that may interfere with the analysis. When the solenoid is in the
compounds of interest elute at the analytical detector. off position the flow of the primary column is sent to the
monitor detector (Fig. 1(a)). When the solenoid is in the on
6.2 Sample Introduction System—Automated liquid injec-
position, the flow of the primary column is sent to the
tion to the split inlet is required. Devices capable of 0.2 µL to
analytical column and subsequently to the analytical detector
2.0 µL injections is suitable.
(Fig. 1(b)). A shunt restrictor is placed across the output of the
6.3 Columns—The precision for this test method was devel- solenoid which provides a trickle of flow to the unswept
oped utilizing fused silica open tubular columns with non-polar section.
polydimethylsiloxane bonded (cross-linked) phase coating and
6.7 The gas chromatograph requires a means to program the
a polyethylene glycol coated fused silica column.
pressures required for the transfer of components from the
6.3.1 Primary Column—An open tubular column with a
primary to the analytical column as well as to control the inlet
non-polar polydimethylsiloxane bonded (cross-linked) phase
pressure during the analysis so as to perform backflush. It is
coating, having 30 m by 0.25 mm with a 0.25 µm film
essential that the gas chromatograph be provided with accurate
thickness, is used as primary column. This column is installed
and reproducible oven temperature control. Control may be
from the split inlet to the microfluidic device. Follow Practice
through hardware or software of the gas chromatograph. In
E1510 for column installation at the split inlet. The column is
addition software is required to integrate the signals and
also inserted to the proper port of the microfluidic device with
perform internal standard and or external standard calculations
an appropriate ferrule. Follow the instructions of the manufac-
as required.
turer of the microfluidic device when inserting the column and
setting the ferrule to the column. Utmost care is required when 6.8 A data system is required to acquire data and to control
making the connection of the ferrule to the device in order not the gas chromatograph’s operational variables. A data system is
to crack the fused silica column. required to perform calibrations and analysis in the internal
6.3.2 Analytical Column—A second open tubular column, standard mode. The data systems require that sample mass and
30 m by 0.25 mm with a film thickness 0.25 µm, containing a internal standard mass be entered. The calculation of response
polyethylene glycol phase which is a polar phase. One end of factors are described in Practice D4626.
this analytical column is inserted into the microfluidic device
and the opposite end is connected to the analytical detector. 7. Reagents and Materials
Observe the same precautions in making the connections as 7.1 Reagent grade chemicals shall be used in all tests.
described in 6.3.1. Unless otherwise indicated, it is intended that all reagents shall

3
 D7920 − 15´1

FIG. 1 (a) Heart-cut System Flow to Monitor Detector

FIG. 1 (b) Heart-cut System Flow to Analytical Detector (continued)

conform to the specifications of the committee on Analytical 7.3 Detector Gases—Hydrogen, air, and nitrogen. The mini-
Reagents of the American Chemical Society, where such mum purity of the gases used should be 99.95 % for the
specifications are available.3 Consult Practice D4307 in the hydrogen and nitrogen. The air should be hydrocarbon-free
preparation of standard blends. grade. Gas purifiers are recommended for the detector gases.
7.2 Carrier Gas—Helium or hydrogen having at least a 7.4 Standards for Calibration and Identification—Standards
minimum purity of 99.95 % can be used as carrier gas. Oxygen of all components to be analyzed are required for establishing
removal systems and gas purifiers should be used. (Warning— identification by retention time as well as for the preparation of
Helium and hydrogen are compressed gases under high pres- calibration standards for quantitative measurements. These
sure). (Warning—Hydrogen carrier gas requires additional materials shall be of known purity and free of the other
safety considerations due to its high flammability and potential components to be analyzed.
for explosions. The use of hydrogen sensors for the detection of 7.4.1 Methanol—(Warning—Flammable and may be harm-
hydrogen leaks in the GC oven is highly recommended. These ful or fatal, if ingested or inhaled.) Minimum purity required of
devices should be capable of shutting the hydrogen flow to the at least 99 % by volume and free of ethanol. It is recommended
gas chromatograph.) that the methanol used in calibration blends be stored over
anhydrous sodium sulfate. Water content of the methanol is
required for the analysis. Refer to Test Method E1064.
3
Reagent Chemicals, American Chemical Society Specifications, American 7.4.2 Ethyl Acetate—(Warning—Flammable and may be
Chemical Society, Washington, DC. For suggestions on the testing of reagents not harmful or fatal, if ingested or inhaled.) This compound is used
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
as the internal standard.
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, 7.4.2.1 The internal standard is added in a constant amount
MD. to all calibration standards containing the analyte of interest. A

4
 D7920 − 15´1
plot of the ratio of the area of analyte to internal standard 7.7 Preparation of Standards for Fuel Methanol (M99):
versus the amount of analyte to internal standard yields a linear 7.7.1 Response Factor Solution—For the analysis of fuel
relationship. The ensuing linear relationship is used to deter- methanol, prepare a standard solution containing the compo-
mine the concentration of the analyte in the sample. nents in 7.4.5 at approximately 50 mg/kg. First prepare a stock
7.4.3 Diluent—1,2-Dimethoxy ethane (>99 % and solution by weighing, to the nearest 0.1 mg, approximately
anhydrous), methanol free, is used for preparation of calibra- 0.100 g of each component listed in 7.4.5 into a 100 mL
tion standards. This diluent shall be free of any compounds that volumetric flask. Add reagent grade methanol as the solvent
coelute with methanol and ethyl acetate. (Warning— and record the mass of methanol. This will yield a stock
Flammable and may be harmful or fatal, if ingested or inhaled.) solution of approximately 1260 mg/kg of each component.
7.4.4 Gasoline—Used alternatively as a diluent and as Further prepare a second solution by pipetting 1.0 mL of the
verification of the absence of interfering compounds. The stock solution and diluting with methanol in a 25 mL volumet-
gasoline shall be free of methanol and ethyl acetate. This can ric flask. Record the mass in each step so as to determine the
be accomplished by analyzing the diluent gasoline as a sample. concentrations by mass. The second solution is approximately
Verify that the chromatograms do not show the presence of any 50 mg/kg and is used to determine the response factors of the
other component that coelutes with methanol or ethyl acetate. impurities. Calculate the concentration of the impurity in the
7.4.5 Impurities in Fuel Methanol (M99)—The following final solution (Ci) in mg/kg using the following equation:
additional chemicals are required to determine the response
~ C i ! 5 ~ @ w 1 ⁄ ~ w 1 1 wm1 ! # 3 w 2 3 106 ! ⁄ ~ w 2 1 wm2 ! (1)
factors of the impurities in the fuel methanol. These chemicals
should be at least of the purity defined in 7.1: ethanol, acetone, where:
isopropanol, n-propanol, 2-butanol, isobutanol, and 1-butanol. w1 = mass of the impurity in the first solution,
(Warning—All of these chemicals are flammable and may be wm1 = the mass of methanol in the first solution,
harmful or fatal, if ingested or inhaled.) w2 = the mass of the aliquot of the first solution, and
wm2 = is the mass of methanol of the second solution.
7.5 Calibration Mixtures—There are two types of calibra-
tion procedures required. One set of calibration mixtures is
used for the analysis of fuel methanol (M99). The other 8. Sampling
calibration mixtures are used for the analysis of methanol in the 8.1 Fuel methanol may be sampled into an open container
methanol fuel blends. since a vapor pressure of less than 21 kPa (3 psi) is expected.
7.5.1 Glassware—Volumetric flasks 25 mL and 100 mL Refer to Practice D4057 for instructions on manual sampling
class A are required. In addition, a 25 mL burette (tolerance from bulk storage into open containers. Stopper the container
0.03 mL class A TD) with 0.1 mL divisions is needed to immediately after drawing the sample.
prepare the calibration standards. A 10 mL burette (graduated
8.2 To minimize loss of hydrocarbon light ends, chill the
in 0.05 mL) is required to pipette the ethyl acetate.
sample (4 ºC or less) before transferring an aliquot into an auto
7.5.2 Check for other impurities such as water. Water cannot
sampler vial. Seal immediately
be determined with sufficient accuracy by most GC methods
and shall be measured by other procedures such as Test
9. Preparation and Verification of Apparatus
Methods D1364 or E1064 and the result used to normalize the
chromatographic value. If any of the impurities found are 9.1 Column Installation—Install the primary column, from
components which are also present in the blend, determine the inlet to the microfluidic device. Install the analytical
their concentrations and make the appropriate corrections. column (wax column) from the device to the analytical
7.6 Preparation of Standards for Methanol in Fuel detector. Consult Practice E1510, which contains information
Analysis—A guide for the preparation of the methanol fuel for installing capillary columns.
blend calibration standards is provided in Table 3. The solu- 9.2 Restrictor Installation—Install the restrictor, (0.1 mm
tions are prepared in 25 mL volumetric flasks. Final volume is I.D. fused silica tubing), from the device to the monitor
fixed to 25 mL by the addition of 1,2-dimethoxyethane or detector. Use a software calculator (available from the web and
gasoline (described in 7.4.4) as the diluent. called “Dean Switch Calculator”) to determine the exact length
7.6.1 In a separate 25 mL volumetric flask, pipette 1.0 mL of of the restrictor. The length will be approximately 78 cm. This
ethyl acetate and dilute to the mark with the solutions prepared restrictor has an equivalent pneumatic resistance as the ana-
in 7.6. These solutions are used to determine the calibration lytical column and its length and diameter is selected to
curve. minimize the analyte’s holdup time.

TABLE 3 Guidefor the Preparation of the Calibration Standards by Volume for the Analysis of Methanol Fuel Blends
Percent Methanol 10 30 40 50 85 90 95 97 99

Methanol (mL) 2.5 7.5 10 12.5 21.25 22.5 23.75 24.25 24.75

1,2 Dimethoxyethane Balance Balance Balance Balance Balance Balance Balance Balance Balance

Total Volume (mL) 25 25 25 25 25 25 25 25 25

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 D7920 − 15´1
9.2.1 Use software (see 9.2) to determine the pressures The recorded chromatogram can be inspected by using the
required for helium or hydrogen carriers at 50 °C oven tem- integration tick marks from the recorded chromatogram as a
perature. For helium carrier, set the flows in the software to guide to select the cut window. Select a time 0.1 min larger
2 mL ⁄min for the primary column and for the analytical than the observed baseline time recovery. These two selected
column set the flow to 3 mL/min which will yield the pressures times constitute the cut window. Repeat the process for the
in Table 1. For hydrogen carrier, set the flows in the software ethyl acetate. At these two time intervals the solenoid valve is
to 2.5 mL ⁄min and 3.5 mL ⁄ min for the primary and analytical switched on and off as shown in Figures 1A and 1B. It is to be
respectively. These settings will yield the pressure settings in emphasized that the cut times are only given as an example
Table 2. since these values maybe different depending on column
9.3 Conditions for Fuel Methanol (M99)—Set the condi- dimension values, pneumatic properties, and oven temperature.
tions for the gas chromatograph as indicated in Table 1 or Table 9.4.1 Enable the solenoid to turn on and off at the selected
2, depending on the carrier gas used. cut time as determined in 9.4.
9.3.1 Ensure that the switching valve for the auxiliary gas 9.4.2 Enable the oven temperature as described in Table 1 or
remains in the off position. Inject 1.0 µL of the calibration Table 2 but maintained the oven at 50 °C for 5.5 min. Inject the
standards for the analysis of fuel methanol as prepared in 7.7.1 sample prepared in 9.4 containing methanol and ethyl acetate.
using the instrument conditions of Table 1 (helium) or Table 2 Record the time necessary for the elution of the ethyl acetate in
(hydrogen). The chromatogram is shown in Fig. 2 (helium) and the analytical column. Add 0.5 min to this time. At this point,
Fig. 3 (hydrogen) where the fuel methanol is analyzed by the the transfer of methanol and ethyl acetate to the analytical
primary column. Record the retention times and verify that the column has been completed. Table 4 gives approximate reten-
retention times are similar to those listed in Table 4. Note that tion times which may differ slightly for different setups.
the conditions of Table 1 and Table 2 may yield slightly 9.5 Pressure and Oven Program for Accelerating the Re-
different retention times. moval of the Matrix—Enable pressure programs for both
9.4 Conditions for Methanol Fuel Blends—Use the calibrat- columns in order to backflush the remaining gasoline compo-
ing solution prepared in 7.6.1 containing 85 % methanol and nents still to be eluted from the primary column at a time after
which contains ethyl acetate and 1,2 dimethoxyethane. Prepare the ethyl acetate has eluted from the analytical column as
the gas chromatograph according to the settings in either Table recorded in 9.4. The pressure program is also used to accelerate
1 or Table 2 if using helium or hydrogen carriers. Program the the elution of gasoline which has entered the analytical
oven to remain isothermal at 50 °C for 5.5 min. Ensure that the column. The time chosen for the beginning is the recorded time
valve remains in the off position. The chromatogram obtained in 9.4.2. This backflush mode is achieved by raising the
from the monitor detector is shown in Fig. 4. A similar pressure of the analytical column to 414 kPa at a high rate (that
chromatogram is obtained when using hydrogen as carrier. The is, 414 kPa/min to 620 kPa/min) while simultaneously lower-
chromatogram is amplified in the data system so as to select the ing the primary column pressure to 6.89 kPa at a similarly high
cut windows. Select a time to the left of the methanol peak rate. Maintain this pressure program until the end of the
where the peak begins to rise, at about 0.1 min before the chromatographic run time. The rise in pressure through the
beginning of the rise. Then select the time where the signal has analytical column hastens the elution of the matrix. At the same
completely returned to the baseline after the methanol peak. time that the pressure programs are enabled, ramp the oven at

NOTE 1—Approximate concentration is 1200 mg/kg each impurity.

FIG. 2 Chromatogram of Fuel Methanol Obtained from Monitor Detector Showing Typical Impurities (Helium Carrier Gas)

6
 D7920 − 15´1

NOTE 1—Approximate concentration is 1200 mg/kg each impurity.

FIG. 3 Chromatogram of Fuel Methanol Obtained From the Monitor Detector Showing Typical Impurities (Hydrogen Carrier Gas)

TABLE 4 Retention Times Obtained for the Analysis of M85 and M99 Using Helium and Hydrogen Carriers
Retention Time (min) for Methanol and Ethyl Acetate in M85 Fuel Blend at 50 °C and
Constant Pressure as per Table 1 (Helium) and Table 2 (Hydrogen)

Component Monitor Column Analytical Column Carrier

Methanol 2.418 4.12 Helium
Ethyl Acetate (I.S.) 3.286 4.903 Helium
Methanol 1.448 2.653 Hydrogen
Ethyl Acetate (I.S.) 1.970 3.142 Hydrogen

Retention Time (min) for the Analysis of Fuel Methanol (M99) Obtained from the Monitor Column

Component Helium Hydrogen

Methanol 2.971 1.44
Propane 2.831 1.39
Ethanol 3.183 1.509
Acetone 3.216 1.567
Isopropanol 3.534 1.579
n-Propanol 3.89 1.736
2-Butanol 3.985 1.911
Ethyl Acetate (I.S.) 4.063 1.96
Isobutanol 4.184 2.054
1-Butanol 4.703 2.308

25 °C/min to 190 °C and hold 2 min. These actions will result 9.6.1 Inject the gasoline used as described in 9.6. Verify the
in a run time of 10 min to 12 min. A blank run with no injection absence of signal at the times corresponding to the elution of
will verify the absence of any residual components. methanol and ethyl acetate. Inspect the chromatogram to verify
9.6 Check of Cut Times with a Methanol Fuel Blend— that there are no peaks merging prior or after the elution of
Prepare a methanol fuel blend by pipetting 16 mL of methanol methanol and the internal standard.
and 1.0 mL of ethyl acetate in a 25 mL volumetric flask. Dilute 9.7 Overloading of the column can cause loss of resolution
to the mark with gasoline described in 7.4.4. Inject this blend for some components. Overloaded peaks are skewed and
under the conditions of Table 1 or Table 2 (helium or hydrogen produce variances in retention times. This can lead to errone-
carrier). Enable the pressure and temperatures programs de- ous component identification. During column evaluations and
scribed in 9.5. Verify that the methanol and ethyl acetate appear split linearity studies, be aware of any peaks that appear front
in the analytical detector as shown in Fig. 5 (helium carrier) skewed, indicating column overload. Note the component size
and Fig. 6 (hydrogen carrier). and avoid conditions leading to this problem during actual

7
 D7920 − 15´1

FIG. 4 Chromatogram of Methanol and Ethyl Acetate Mixture for Determining Cut Times (Helium Carrier)

FIG. 5 Chromatogram Obtained from Analytical Detector (Lower Chromatogram) after Executing Heart-cut at Times Indicated in Upper
Chromatogram (Helium) Gasoline Matrix

analysis. Refer to Practice E594 for further guidance. Use split percent impurities of the oxygenates used. Whenever possible,
ratio of 500:1 for both carriers due to the large concentrations use stocks having at least 99.5 % purity or higher.
of methanol. 10.1.1 For the 1,2-dimethoxyethane used in the standard
preparation, it is important that the 1,2-dimethoxyethane be
10. Calibration and Standardization examined for the absence of signal where methanol and ethyl
10.1 Calibration for Analysis of Methanol in Methanol Fuel acetate elute in the chromatogram. Inject 0.2 µL of the
Blend Analysis, when preparing standards correct for the 1,2-dimethoxyethane using the cut times determined in 9.6.

8
 D7920 − 15´1

FIG. 6 Chromatogram Obtained from Analytical Detector (Lower Chromatogram) of Methanol Fuel Blend Injection after Executing Heart-
cut at Times Indicated in Upper Chromatogram (Hydrogen Carrier)

Verify the absence of peaks at the corresponding times of 10.4 Record the areas for the methanol and the internal
methanol and ethyl acetate in the analytical column. standard.
10.2 Use the standard solutions prepared in 7.6.1. These 10.5 Obtain from the data system, the area ratio of the
standards cover the range from 10 % to 99 % methanol by methanol to the ethyl acetate. Obtain the ratio of the amount of
volume. methanol to ethyl acetate from the data of the preparation of the
10.3 Inject 0.2 µL from the calibration solutions prepared in calibration standards (Table 3).
7.6.1 in ascending order of the methanol content and verify that
the solenoid valve is switched as per the established cut times 10.6 A plot of the area ratios versus the amount ratios is a
in 9.4 causing the transfer of the methanol and ethyl acetate to linear relationship as seen in Fig. 7 (seven levels) using helium
the analytical column. as carrier and Fig. 8 (9 levels) using hydrogen as carrier. Verify

FIG. 7 Linear Plot of Area Ratios versus Volume Amount Ratios for Methanol (Helium Carrier))

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 D7920 − 15´1

FIG. 8 Linear Plot of Area Ratios versus Amount Ratios (V/V) for Methanol (Hydrogen Carrier) Covering Range 10 % to 99 % Methanol

that the calibration has a correlation coefficient of at least lent. Measure the ethanol and methanol concentrations using
0.999. Force the calibration through the origin. the procedure outlined in Section 12. Confirm the performance
10.7 In the event that an electronic data acquisition system of the instrument or the test procedure after each calibration
is not available use spreadsheet or other software to carry out and on each day of use thereafter. Include at least one quality
the calculations as shown below. The spreadsheet will aid in control sample of known ethanol and methanol content.
determining a linear regression analysis which yields a linear 11.1.1 Standard(s) of known concentration may be obtained
equation as described in 10.6. from vendor, a cross-check program, or may be prepared
gravimetrically as shown in Table 3; use the density of
Ai
As
5 S DS D
mi
ms
1
RRF
(2) methanol to determine the volume.

where: 12. Gas Chromatographic Analysis Procedure

Ai = area of the methanol standard, 12.1 Analysis of Fuel Methanol—Set the instrument operat-
As = area of the ethyl acetate, ing conditions depending on the carrier gas used. See Table 1
mi = volume percent of methanol in the standard, and or Table 2. Ensure that the valve will not be switched.
ms = the volume percent of the ethyl acetate. 12.1.1 Inject 1.0 µL of the sample of fuel methanol with
The constant 1/RRF is the slope. RRF is the relative identical conditions as the injection of the calibration stan-
response factor for methanol relative to ethyl acetate. dards. The chromatograms obtained should be similar to the
10.8 Calibration for Fuel Methanol—Prepare the calibra- ones shown in Fig. 2 and Fig. 3. Record the areas of the
tion standards as described in 7.7.1. Set the instrument to the impurities and the retention time of the impurities for identi-
conditions in Table 1 (helium) or Table 2 (hydrogen). Ensuring fication. Note the retention time of any peak which cannot be
that the valve remains in the off position, inject the response identified.
factor solution containing the possible impurities. A typical 12.2 Analysis of Methanol Fuel Blends—Into a 25 mL
chromatogram is shown in Fig. 2 and Fig. 3 for helium and volumetric flask pipette 1.0 mL of ethyl acetate. Fill to the
hydrogen, respectively. Record all the areas for the impurities mark with the methanol fuel blend to be analyzed. Inject 0.2 µL
added to the methanol. Using a data acquisition system or of the sample under the conditions of Table 1 or Table 2
utilizing Eq 3below determine the response factors for the (helium or hydrogen carrier). Record the area of methanol and
components added to the methanol. This calibration is carried ethyl acetate in order to calculate percent methanol in the
out on a mass basis. sample.
~ RF! I 5 ~ m i ! ⁄ ~ A i ! (3)
13. Calculation
where:
(RF)1 = response factor of the impurity, 13.1 Fuel Methanol—Obtain the areas for the identified
mi = concentration of the impurity in mg/kg, and impurities in the fuel methanol. Utilizing the data system in the
Ai = area of the impurity. external standard mode, calculate the percent of each impurity
identified. For those impurities not identified apply the relative
11. Quality Control response factor of the nearest identified impurity.
11.1 Conduct a regular statistical quality assurance (quality 13.1.1 The mass percent of each impurity is calculated by
control) program, monitoring both precision and accuracy, in Eq 4.
accordance with the techniques of Practice D6299 or equiva- m i 5 ~ R F ! 1 ~ A i ! 3 1022 (4)

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 D7920 − 15´1
where: 13.4 If it is desired to report a percent mass of methanol in
mi = percent mass of the impurity, the methanol fuel use the following equation:
Ai = area of the impurity, and percent w =~ percent V ⁄ D f ! 3 0.7918 (6)
(RF)1 = response of the impurity.
where:
13.1.2 The percent mass of methanol is determined by
difference from the following equation: percent w = percent mass of methanol in the fuel,
Df = relative density of the fuel at 15.5 °C ⁄15.6 °C
A 5 100 2 percent mass W H202 @ ~ Σ mi percent! # (5) (60 °F ⁄60 °F), and
where: percent V = percent volume as determined by the test
method.
A = percent mass methanol,
(∑ mi percent) = sum of the percent mass of the impurities
determined in 13.1.1, and 14. Report
WH20 = percent mass water in the methanol. 14.1 Report the volume percent of methanol in methanol
13.1.3 Consult Test Methods D1364 and E1064 for the fuel blends to the nearest 0.01 % as determined in Section 13;
percent water determination. report the mass percent of fuel methanol to the nearest 0.01 %.
Use the guidelines of Practice E29 for the proper significant
13.2 Methanol Fuel Blend—For the analysis of methanol in figures.
a methanol fuel blend, set the data system in the internal
standard mode utilizing the calibration levels as determined in 15. Precision and Bias
10.7. From the area obtained from the injection of methanol
sample and using the recorded areas of methanol and ethyl 15.1 Precision—The precision of this test method is to be
acetate obtained in section 12.2, interpolate the percent metha- determined by an interlaboratory study (ILS).
nol utilizing Eq 2. 15.2 A temporary repeatability standard deviation as defined
13.3 If a data system is not available use a spread sheet to in ASTM Form and Style Manual (A21.5.1) was obtained by
plot the area ratios versus the amount ratios as shown in 10.7. analyzing samples of methanol fuel blends as well as fuel
Use the spreadsheet software to determine the linear regression methanol and these interim values are listed in Table 5 and
coefficient and the calibration curve. Solve for the amount of Table 6 using helium and hydrogen as carrier gases, respec-
methanol. tively. A proper ILS will be completed by 2020.

TABLE 5 Repeatability Obtained for Analysis of Methanol Fuel Blends Obtained from Three Different Samples using Helium and
Hydrogen as Carriers
Helium Carrier
Volume Percent
Run Sample 1 Sample 2 Sample 3
1 71.30 88.96 85.26
2 70.72 89.48 85.24
3 71.48 88.60 85.22
4 71.38 89.39 85.33
5 71.63 89.41 85.32
6 71.70 89.38 85.18
7 71.57 89.04 85.29
8 71.69 88.76 85.38

Average 71.43 89.13 85.28

Std.Dev. 0.30 0.31 0.07
percent RSD 0.42 0.35 0.08
Repeatability Std.Dev. 0.74 0.77 0.16

H2 Carrier
Volume Percent
Run Sample 4 Sample 5 Sample 6 Sample 7
1 86.73 85.76 85.43 99.2
2 86.72 85.11 85.45 99.42
3 87.24 85.1 85.48 99.45
4 87.25 85.32 85.53 99.21
5 87.25 84.75 85.51 99.31
6 87.31 85.31 85.6 99.37
7 87.23 85.24 85.52 99.45
8 87.11 85.44 85.41 99.25

Average 87.11 85.25 85.49 99.33

Std.Dev. 0.24 0.27 0.06 0.10
percent RSD 0.28 0.32 0.07 0.11
Repeatability Std.Dev. 0.59 0.67 0.15 0.26

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 D7920 − 15´1
TABLE 6 Repeatability of Fuel Methanol Helium and Hydrogen 15.2.1 In Table 5, the repeatability standard deviation asso-
Carrier ciated with two different instruments (older and newer) are
NOTE 1—Fuel methanol made from reagent grade methanol. listed and because the difference was determined to be statis-
NOTE 2—Not corrected for water.
tically significant the standard deviations (sd), degrees of
freedom (df) and ranges are listed in Table 7.
Repeatability of Fuel Methanol
mass percent 15.3 At present, no bias statement can be made since this
Helium Hydrogen test method has not been evaluated using an industry-accepted
98.69 97.93
98.69 98.21 Certified Reference Material (CRM).
98.67 98.19
98.68 98.35 16. Keywords
98.69 98.37
98.68 97.99
16.1 fuel methanol; impurities in methanol; methanol con-
98.68 98.18 tent in gasoline; methanol fuel; methanol-gasoline blends
Average 98.68 97.17 TABLE 7 Statistical Comparison of Data of Table 5
Std.Dev. 0.01 0.17
sd df range
percent STD 0.01 0.17
new inst. 0.06 49 70–97
Rep. Std. 0.02 0.41
old inst. 0.25 21 71–94

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