ASTM D5441 - 21 (2025) 用气相色谱法分析甲基叔丁基醚（MTBE）的标准试验方法

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Designation: D5441 −21 (Reapproved 2025)

Standard Test Method for

Analysis of Methyl Tert-Butyl Ether (MTBE) by Gas

Chromatography

This standard is issued under the ﬁxed designation D5441; the number immediately following the designation indicates the year of

original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A

superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope

1.1 This test method covers the determination of the purity

of methyl tert-butyl ether (MTBE) by gas chromatography. It

also provides a procedure to measure impurities in MTBE such

as C

to C

oleﬁns, methyl, isopropyl and tert-butyl alcohols,

methyl sec-butyl and methyl tert-amyl ethers, acetone, and

methyl ethyl ketone. Impurities are determined to a minimum

concentration of 0.02 % by mass.

1.2 This test method is not applicable to the determination

of MTBE in gasoline.

1.3 Water cannot be determined by this test method and

must be measured by a procedure such as Test Method D1364

and the result used to normalize the chromatographic values.

1.4 A majority of the impurities in MTBE is resolved by the

test method, however, some co-elution is encountered.

1.5 This test method is inappropriate for impurities that boil

at temperatures higher than 180 °C or for impurities that cause

poor or no response in a ﬂame ionization detector, such as

water.

1.6 The values stated in SI (metric) units of measurement

are preferred and used throughout the standard.

1.6.1 Exception—Alternate units, in common usage, are

also provided to improve clarity and aid the user of this test

method.

1.7 This standard does not purport to address all of the

safety concerns, if any, associated with its use. It is the

responsibility of the user of this standard to establish appro-

priate safety, health, and environmental practices and deter-

mine the applicability of regulatory limitations prior to use.

1.8 This international standard was developed in accor-

dance with internationally recognized principles on standard-

ization established in the Decision on Principles for the

Development of International Standards, Guides and Recom-

mendations issued by the World Trade Organization Technical

Barriers to Trade (TBT) Committee.

2. Referenced Documents

2.1 ASTM Standards:

D1364 Test Method for Water in Volatile Solvents (Karl

Fischer Reagent Titration Method)

D3700 Practice for Obtaining LPG Samples Using a Float-

ing Piston Cylinder

D4057 Practice for Manual Sampling of Petroleum and

Petroleum Products

D4175 Terminology Relating to Petroleum Products, Liquid

Fuels, and Lubricants

D4307 Practice for Preparation of Liquid Blends for Use as

Analytical Standards

D4626 Practice for Calculation of Gas Chromatographic

Response Factors

E355 Practice for Gas Chromatography Terms and Relation-

ships

E594 Practice for Testing Flame Ionization Detectors Used

in Gas or Supercritical Fluid Chromatography

3. Terminology

3.1 Deﬁnitions—This test method makes reference to many

common gas chromatographic procedures, terms, and relation-

ships. Detailed deﬁnitions of these and other terms used in this

test method can be found in Practices E355 and E594, and

Terminology D4175.

3.2 Deﬁnitions of Terms Speciﬁc to This Standard:

3.2.1 C

to C

oleﬁns, n—common oleﬁn impurities in

MTBE are unreacted feedstock and dimers or trimers of feed

such as trimethylpentene or pentamethylheptene.

4. Summary of Test Method

4.1 A representative aliquot of the MTBE product sample is

introduced into a gas chromatograph equipped with a methyl

silicone bonded phase fused silica open tubular column.

This test method is under the jurisdiction of ASTM Committee D02 on

Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of

Subcommittee D02.04.0L on Gas Chromatography Methods.

Current edition approved Oct. 1, 2025. Published October 2025. Originally

approved in 1993. Last previous edition approved in 2021 as D5441 – 21. DOI:

10.1520/D5441-21R25.

For referenced ASTM standards, visit the ASTM website, www.astm.org, or

contact ASTM Customer Service at www.astm.org/contact. For Annual Book of

ASTM Standards volume information, refer to the standard’s Document Summary

page on the ASTM website.

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the

Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

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Helium carrier gas transports the vaporized aliquot through the

column where the components are separated by the chromato-

graphic process. Components are sensed by a ﬂame ionization

detector as they elute from the column.

4.2 The detector signal is processed by an electronic data

acquisition system or integrating computer. Each eluting com-

ponent is identiﬁed by comparing its retention time to those

established by analyzing standards under identical conditions.

4.3 The concentration of each component in mass percent is

determined by normalization of the peak areas after each peak

area has been corrected by a detector response multiplication

factor. The detector response factors are determined by ana-

lyzing prepared standards with concentrations similar to those

encountered in the sample.

5. Signiﬁcance and Use

5.1 The presence of impurities in MTBE product can have a

deleterious effect upon the value of MTBE as a gasoline

additive. Oxygenate and oleﬁn contents are of primary con-

cern. This test method provides a knowledge of the composi-

tion of MTBE product. This is useful in the evaluation of

process operations control, in the valuation of the product, and

for regulatory purposes.

5.2 Open tubular column gas chromatography with a ﬂame

ionization detector, used by the test method, is a technique that

is sensitive to the contaminants commonly found in MTBE,

and a technique that is widely used.

6. Interferences

6.1 Cyclopentane and 2,3-dimethylbutane have been ob-

served to co-elute with MTBE. However, these are not com-

monly found impurities in MTBE.

7. Apparatus

7.1 Gas Chromatograph—Instrumentation capable of oper-

ating at the conditions listed in Table 1. A heated ﬂash

vaporizing injector designed to provide a linear sample split

injection (that is, 200:1) is required for proper sample intro-

duction. Carrier gas controls must be of adequate precision to

provide reproducible column ﬂows and split ratios in order to

maintain analytical integrity. Pressure control devices and

gauges must be designed to attain the linear velocity required

in the column used (for example, if a 150 m column is used, a

pressure of approximately 550 kPa (80 psig) is required). A

hydrogen ﬂame ionization detector with associated gas controls

and electronics, designed for optimum response with open

tubular columns, is required.

7.2 Sample Introduction—Manual or automatic liquid sy-

ringe sample injection to the splitting injector is employed.

Devices capable of 0.1 µL to 0.5 µL injections are suitable. It

should be noted that inadequate splitter design, or poor

injection technique, or both can result in poor resolution.

Overloading of the column can also cause loss of resolution for

some components and, since overloaded peaks are skewed,

variation in retention times. Watch for any skewed peaks that

indicate overloading during column evaluation. Observe the

component size and where possible, avoid conditions leading

to this problem during the analyses.

7.3 Open Tubular Column

—This test method utilizes a

fused silica open tubular column with non-polar methyl sili-

cone bonded (cross-linked) phase internal coating such as one

of the following:

Column length 50 m 100 m 150 m

Film thickness 0.5 µm 0.5 µm 1.0 µm

Internal diameter 0.20 mm 0.25 mm 0.25 mm

Other columns with equal or greater resolving power may be

used. A minimum resolution between trans-2-pentene and

tert-butanol, and between cis-2-pentene and tert-butanol of 1.3

is required. The 150 m column is expected to decrease the

likelihood of co-elution of impurities.

7.4 Electronic Data Acquisition System—Any data acquisi-

tion and integration device used for quantiﬁcation of these

analyses must meet or exceed these minimum requirements:

7.4.1 Capacity for at least 50 peaks per analysis,

7.4.2 Normalized area percent calculations with response

factors,

7.4.3 Identiﬁcation of individual components based on re-

tention time,

7.4.4 Noise and spike rejection capability,

7.4.5 Sampling rate for fast (<1 s) peaks,

7.4.6 Positive and negative sloping baseline correction,

7.4.7 Peak detection sensitivity compensation for narrow

and broad peaks, and

7.4.8 Non-resolved peaks separated by perpendicular drop

or tangential skimming as needed.

8. Reagents and Materials

8.1 Carrier Gas, helium, 99.99 % pure. (Warning—

Compressed gas under high pressure.)

8.2 Fuel Gas, hydrogen, 99.99 % pure. (Warning—

Extremely ﬂammable gas under pressure.)

Petrocol DH series columns from Supelco, Inc., Bellefonte, PA were used to

obtain the retention data and example chromatogram shown in this standard. Other

suitable columns are available commercially.

TABLE 1 Typical Operating Conditions

Column Temperature Program

Column length 50 m 100 m 150 m

Initial temperature 40 °C 50 °C 60 °C

Initial hold time 13 min 13 min 13 min

Program rate 10 °C ⁄min 10 °C ⁄min 10 °C ⁄min

Final temperature 180 °C 180 °C 180 °C

Final hold time 3 min 7 min 20 min

Injector

Temperature 200 °C

Split ratio 200:1

Sample size 0.1 to 0.5 µL

Detector

Type ﬂame ionization

Temperature 250 °C

Fuel gas hydrogen ('30 mL/min)

Oxidizing gas air ('300 mL/min)

Make-up gas nitrogen ('30 mL/min)

Carrier Gas

Type

Average linear velocity

helium

20 cm ⁄s to 24 cm ⁄s

D5441 − 21 (2025)

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8.3 Oxidant, air, oil free. (Warning—Compressed gas un-

der high pressure.)

8.4 Make-Up Gas, nitrogen, 99.99 % pure. (Warning—

Compressed gas under high pressure.)

8.5 Reference Standards:

8.5.1 tert-Amyl methyl ether,

4,5

(Warning—Flammable

liquid. Harmful if inhaled.)

8.5.2 Butane, (Warning—Flammable liquid. Harmful if

inhaled.)

8.5.3 tert-Butanol, (Warning—Flammable liquid. Harmful

if inhaled.)

8.5.4 sec-Butyl methyl ether,

6,5

(Warning—Flammable

liquid. Harmful if inhaled.)

8.5.5 4,4-Dimethyl-2-neopentyl-1-pentene,

7,5

(Warning—

Flammable liquid. Harmful if inhaled.)

8.5.6 Isobutylene, (Warning—Flammable liquid. Harmful

if inhaled.)

8.5.7 Methanol, (Warning—See Note 1.)

NOTE 1—Warning: Toxic Flammable Liquid. Harmful if inhaled or

ingested.

8.5.8 2-Methyl-2-butene,

7,5

(Warning—Flammable liquid.

Harmful if inhaled.)

8.5.9 Methyl tert-butyl ether, 99 + % pure,

8,5

(Warning—

Flammable liquid. Harmful if inhaled.)

8.5.10 2,2,4,6,6-Pentamethyl-3-heptene,

7,5

(Warning—

Flammable liquid. Harmful if inhaled.)

8.5.11 n-Pentane, (Warning—Flammable liquid. Harmful

if inhaled.)

8.5.12 cis-2-Pentene, (Warning—Flammable liquid. Harm-

ful if inhaled.)

8.5.13 trans-2-Pentene, (Warning—Flammable liquid.

Harmful if inhaled.)

8.5.14 2,4,4-Trimethyl-1-pentene, (Warning—Flammable

liquid. Harmful if inhaled.)

8.5.15 2,4,4-Trimethyl-2-pentene, (Warning—Flammable

liquid. Harmful if inhaled.)

8.5.16 1 % Contaminant Standard,

9,5

contains 1.0 % of

some of the contaminants in MTBE, (Warning—Flammable

liquid. Harmful if inhaled.)

8.5.17 0.1 % Contaminant Standard,

9,5

contains 0.1 % of

some of the contaminants in MTBE, (Warning—Flammable

liquid. Harmful if inhaled.)

9. Sampling

9.1 MTBE can be sampled either in a ﬂoating piston

cylinder or into an open container since vapor pressures less

than 70 kPa (10 psi) are expected.

9.1.1 Cylinder Sampling—Refer to Practice D3700 for in-

structions on transferring a representative sample from a source

into a ﬂoating piston cylinder. Add inert gas to the ballast side

of the piston to achieve a pressure of 310 kPa (45 psi) above

the vapor pressure of the sample.

9.1.2 Open Container Sampling—Refer to Practice D4057

for instructions on manual sampling from bulk storage into

open containers. Stopper container immediately after drawing

sample.

9.2 Preserve the sample by cooling to approximately 4 °C

and by maintaining that temperature until immediately prior to

analysis.

9.3 Transfer an aliquot of the cooled sample into a pre-

cooled septum vial, then seal appropriately. Obtain the test

specimen for analysis directly from the sealed septum vial, for

either manual or automatic syringe injection.

10. Preparation of Apparatus

10.1 Install and condition column in accordance with manu-

facturer’s or supplier’s instructions. After conditioning, attach

column outlet to ﬂame ionization detector inlet and check for

leaks throughout the system. When leaks are found, tighten or

replace ﬁttings before proceeding.

10.2 Adjust the carrier gas ﬂow rate so that an average

linear velocity at the starting temperature of the run is between

21 cm ⁄s and 24 cm ⁄s, as determined in Eq 1. Flow rate

adjustment is made by raising or lowering the carrier gas

pressure (head pressure) to the injector. The following starting

point pressures can be useful to adjust the carrier gas ﬂow:

Column length 50 m 100 m 150 m

Starting point pressure, kPa (psig) 262 (38) 275 (40) 552 (80)

10.2.1 Average Linear Gas Velocity:

ave

5L/t

(1)

where:

L= the length of the column in cm, and

= the retention time in seconds of methane.

10.3 Adjust the operating conditions of the gas chromato-

graph to conform to the list in Table 1. Turn on the detector,

ignite the ﬂame, and allow the system to equilibrate.

10.4 When the method is ﬁrst set up, ensure that the FID is

not saturated. Plot the peak area versus MTBE concentration

for prepared standards in the concentration range of interest. If

the plot is not linear, increase the split ratio, or use a less

sensitive detector range, or both.

11. Column Evaluation and Optimization

11.1 In order to establish that the column/temperature pro-

gram will perform the required separation, the resolution

between cis-2-pentene and tert-butanol and between trans-2-

pentene and tert-butanol must be determined. The retention of

The sole source of supply of the apparatus known to the committee at this time

is Sigma-Aldrich Chemical Company, Inc., Milwaukee, WI. A 96 % pure sample

obtained from Sigma-Aldrich was the highest purity found.

If you are aware of alternative suppliers, please provide this information to

ASTM International Headquarters. Your comments will receive careful consider-

ation at a meeting of the responsible technical committee,

which you may attend.

The sole source of supply of the apparatus known to the committee at this time

is Farcham Laboratories, Gainesville, FL.

The sole source of supply of the apparatus known to the committee at this time

is Organic Technologies (formerly Wiley Organics), P.O. Box 640, 1245 S. 6th St.,

Coshocton, OH 43812.

The sole source of supply of the apparatus, HPLC grade MTBE, known to the

committee at this time is from Aldrich Chemical Company, Inc., Milwaukee, WI.

The sole source of supply of the apparatus, reference samples that contain only

contaminants boiling above ambient, known to the committee at this time is

Supelco, Inc., Bellefonte, PA.

D5441 − 21 (2025)

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标签： #标准试验 #试验方法 #标准试验方法

摘要：

本文档详细介绍了ASTM D5441 - 21 (2025)标准，即使用气相色谱法分析甲基叔丁基醚（MTBE）的标准试验方法。该标准为石油化工、燃料添加剂及环境检测领域的专业人员提供了精确测定MTBE纯度和杂质的权威操作指南。通过遵循本标准，实验室能够确保测试结果的重复性和准确性，满足燃料质量控制和法规合规要求。本内容适合从事油品分析、化工研发及质量检测的技术人员参考，有助于提升MTBE分析流程的标准化水平。

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ASTM D5441 - 21 (2025) 用气相色谱法分析甲基叔丁基醚（MTBE）的标准试验方法

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