⛽ Determination of individual organic oxygenate compounds (C1–C5 alcohols, ethers MTBE, ETBE, TAME, ETAE, ketones) in the range 0,17–15 % (m/m) and of total organically bound oxygen up to 3,7 % (m/m) in unleaded petrol with a final boiling point not greater than 220 °C — the first capillary column isolates the oxygenates, the second separates them, flame ionisation detection (FID), calibration with an internal standard, result in % (m/m) or % (V/V), PN-EN 13132

Petrochemistry PN-EN 13132

Overview

WHAT THE STANDARD COVERS. Scope from the PKN catalogue card of PN-EN 13132:2005 (Polish version), in full (our translation): “A method is specified for the quantitative determination of individual organic oxygenate compounds by gas chromatography using a column in the range from 0,17 percent (m/m) to 15 percent (m/m) and of total organically bound oxygen content up to 3,7 percent (m/m) in unleaded petrol whose boiling temperature does not exceed 220 degrees C. Sampling, reagents and materials, apparatus, procedure, calculation of results and precision of the method are given”. We read the text of the standard in the sample of SIST EN 13132:2000 — a scan of EN 13132:2000 (March 2000) from the title page through the foreword and Clauses 1–7 up to and including 8.3, read from the page images. Outside the sample remain the rest of the calculation (including total oxygen), expression of results, precision, test report and Annexes A (normative — densities of the compounds) and B (informative — column switching technique and recommended columns).

ACCORDING TO THE TEXT OF EN 13132:2000 (foreword, Clauses 1–8.3). The standard was prepared by CEN/TC 19 “Petroleum products, lubricants and related products” (secretariat NNI); approved by CEN on 14 February 2000. Scope (1): gas chromatographic method using column switching for the quantitative determination of individual organic oxygenate compounds in the range 0,17 % (m/m) to 15 % (m/m) and total organically bound oxygen up to 3,7 % (m/m) in unleaded petrol having a final boiling point not greater than 220 °C (note 1 — the final boiling point can be measured according to prEN ISO 3405:1998; note 2 — “% (m/m)” and “% (V/V)” represent the mass fraction and the volume fraction respectively); the standard is applicable to the determination of oxygen-containing compounds and total oxygen in petrol in line with EU Directives (footnote: 85/210/EEC on the lead content of petrol and 85/536/EEC on crude-oil savings through the use of substitute fuel components in petrol). References (2): EN ISO 3170 (manual sampling), EN ISO 3171 (automatic pipeline sampling), EN ISO 3675 (density by hydrometer), EN ISO 3696 (water for laboratory use), EN ISO 3838 (density by pyknometer), EN ISO 12185 (density by oscillating U-tube). Principle (3): organic oxygenates are isolated from the sample on a first capillary column, separated on a second capillary column and detected individually with a flame ionisation detector (note — guidance on column switching in Annex B). Reagents (4): only of recognized analytical grade and water of grade 3 according to EN ISO 3696; carrier gas (4.1) — hydrogen, helium or nitrogen free of hydrocarbons (warning — hydrogen mixed with air is explosive at concentrations from about 4 % (V/V) to 75 % (V/V); all joints and lines carrying hydrogen shall be gas tight to prevent leakage of hydrogen into a confined space); reagents for calibration samples (4.2) not less than 99,0 % (m/m) pure, in any combination: methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol, butan-2-ol, 2-methylpropan-2-ol (TBA), 2-methylpropan-1-ol, pentan-2-ol, methyl tert-butyl ether (MTBE), methyl tert-pentyl ether (TAME), ethyl tert-pentyl ether (ETAE), acetone, butanone (MEK), ethyl tert-butyl ether (ETBE); internal standard (4.3) — one of the reagents in 4.2, and if all of them are likely to be present in the sample, a different organic oxygenate of the same purity and similar volatility; petrol containing no organic oxygenates detectable by this method, or n-heptane (4.4). Apparatus (5): gas chromatograph with a means for column switching, a programmable oven temperature controller (or controllers for dual-oven chromatographs) and an FID (note — a system made entirely of glass from the injection port to the detector is recommended, since petrol may contain organic oxygenates causing corrosion and changes of retention times in metal systems); two capillary columns (recommended in Annex B) coated with a suitable phase so that the resolution between the components and between the components and the matrix after elution from the second column is at least 1, where R = 1,18 · (t′B − t′A) / (wA + wB), t′ being the retention times and w the peak widths at half-height, in seconds (Figure 1); carrier gas flow controller; recorder or integrator giving peak areas; injection device; test sample container normally of 10–100 ml with a self-sealing rubber septum coated with PTFE. Sampling (6): unless otherwise specified in the commodity specification, according to EN ISO 3170 or EN ISO 3171 or national standards or regulations. Procedure (7): the apparatus is set up according to the manufacturer’s instructions, and the pressure and flow of the carrier gas are adjusted to meet the resolution of 5.1.2; calibration (7.2) — the calibration sample is prepared from weighed organic oxygenates and the internal standard, diluted to a known mass with petrol or n-heptane (note — the calibration sample should contain the same oxygenates in similar proportions as the sample under test); a quantity is injected that does not exceed the capacity of the columns or impair the linearity of the detector, retention times are recorded and the calibration factor fi = (mi · Ast) / (Ai · mst) is calculated for each component, m being masses in grams and A peak areas in microvolt-seconds or square millimetres; density of the sample at 15 °C (7.3) is determined according to EN ISO 3675, EN ISO 3838 or EN ISO 12185 to 0,1 kg/m³; preparation of the test sample (7.4) — the sample is cooled to 5–10 °C, the container with its septum is weighed to 0,1 mg without sealing, the internal standard is transferred into it and weighed again — the mass of internal standard shall be 2–5 % (m/m) of the sample, not less than 0,050 g; then normally 5–100 ml of the cooled sample is transferred, the container is sealed immediately with the septum, weighed to 0,1 mg, the sample mass and the internal standard content as a percentage by mass are recorded, and the contents are mixed by shaking until homogeneous; injection (7.5) — a quantity of the prepared sample that does not exceed the capacity of the columns or impair the linearity of the detector; components are identified by their retention times from calibration (7.6). Calculation (8.1–8.3): component mass mi = Ai · fi · mst / Ast; mass fraction ωi = mi / ms · 100; volume fraction φi = Vi / Vs · 100, where the component volume Vi = mi · 1000 / ρi from the densities of the components at 15 °C given in Annex A, and the sample volume Vs from its density (7.3).

STATUS (catalogue cards as of 03.10.2026). The card of PN-EN 13132:2005 (Polish version, published 29-07-2005, 23 pages, price group L) has no “Withdrawn” header: Chemical Sector, KT 222 Petroleum Products and Similar Products of Biological and Synthetic Origin, ICS 75.160.20, “Introduces: EN 13132:2000 [IDT]”, “Replaces: PN-EN 13132:2002 - English version”. The card of PN-EN 13132:2002 (English version, 15-09-2002) has a “Withdrawn” header with withdrawal date 29-07-2005 and “Replaced by: PN-EN 13132:2005”. The PKN search engine (query “PN-EN 13132”, 03.10.2026) shows these two cards and cards of PN-EN ISO 13132 — a different document, which we do not discuss here. European document: the Slovenian SIST EN 13132:2000 (identical to EN 13132:2000) has the status “Published” in the iTeh catalogue (read 03.10.2026).

HOW MANY LABORATORIES AND IN WHAT FORM (copy of the accreditation scope database, data up to 17.09.2026, read 03.10.2026). The number 13132 appears in 20 records at 8 laboratories: AB 009, AB 079, AB 103, AB 387, AB 474, AB 484, AB 773, AB 1278. In the current scopes on the PCA website (read 03.10.2026, issues from 18.02.2026 to 29.09.2026) AB 079, AB 103, AB 484 and AB 1278 give “PN-EN 13132:2005”, AB 009, AB 387 and AB 773 — the designation alone without year; AB 387 has the item in three places of the document, AB 484 in seven. For AB 474 the PCA website does not provide a scope document — here we rely only on the database copy (2005 edition). The “Laboratories” tab (“PN-EN 13132”) shows all 8 laboratories; checked with the tab query on the production server labcoda.pl on 03.10.2026.

WHAT THE LABORATORIES TEST (items in PCA scopes). “Content of organic oxygenate compounds” of unleaded petrol, at AB 009 also of liquid biohydrocarbons for spark-ignition engines and motor petrol with bioethanol, at AB 1278 also of petrol components; in all documents it is accompanied by “Total organically bound oxygen content (calculated)”, and the technique is “Gas chromatography with flame ionisation detection (GC-FID)”. Ranges: (0,17–15) % (V/V) (AB 103), (0,17–15,0) % (V/V) (AB 484, AB 1278), (0,17–15,0) % (m/m), % (V/V) (AB 079 and one item of AB 484), (0,10–15,0) % (m/m) and (0,10–15,0) % (V/V) (AB 009), (0,2–24,0) % (V/V) (AB 773); AB 387 gives no range. Next to it are vapour pressure according to PN-EN 13016-1, benzene content according to PN-EN 12177 and vapour lock index according to PN-EN 228.

WHERE A SEEMINGLY CORRECT RESULT IS EASY TO GET. Range: the standard covers individual compounds from 0,17 % (m/m) to 15 % (m/m) and total oxygen up to 3,7 % (m/m), in petrol with a final boiling point up to 220 °C (1) — the lower limit of 0,10 % (AB 009) lies below the range of the standard, and the upper limit of 24,0 % (V/V) (AB 773) is expressed in a different unit from the upper limit of the standard (15 % (m/m)), so it cannot be compared directly with the range of the standard. Unit: a result in % (V/V) requires the density of the sample at 15 °C (7.3) and the densities of the components from Annex A (8.3) — without them there is only a result in % (m/m). Internal standard: it must not be a compound present in the sample (4.3), and its mass shall be 2–5 % (m/m) of the sample and at least 0,050 g (7.4). Preparation: the sample is cooled to 5–10 °C and sealed immediately with the septum, and all weighings are made to 0,1 mg (7.4). Calibration: the calibration sample should contain the same compounds in similar proportions as the sample under test (note to 7.2), and the injected quantity must not exceed the capacity of the columns or impair the linearity of the detector (7.2, 7.5). Separation: resolution after the second column at least 1 — also relative to the matrix (5.1.2); the standard recommends a glass system, because in metal systems oxygenates may cause corrosion and changes of retention times (note to 5.1.1), and identification is based precisely on retention times (7.6).

WHAT WE DO NOT GIVE. We do not have the rest of Clause 8 (including the calculation of total oxygen), expression of results, precision, test report or Annexes A and B — so we give neither densities of the components, the formula for total oxygen, repeatability and reproducibility, recommended columns nor column switching conditions.

Method principle

The first capillary column isolates the organic oxygenates from the petrol; after switching they pass to the second capillary column, where they are separated and determined individually with a flame ionisation detector; the amount is calculated from peak areas relative to the added internal standard and the calibration factors, in % (m/m), and through densities in % (V/V).

Applications

• Unleaded petrol — individual alcohols, ethers and ketones 0,17–15 % (m/m) and total oxygen up to 3,7 % (m/m), final boiling point up to 220 °C (scope of the standard); 8 laboratories in PCA scopes
• Liquid biohydrocarbons for spark-ignition engines, motor petrol with bioethanol, petrol components — in PCA scopes
• Petrol testing together with vapour pressure (PN-EN 13016-1), benzene (PN-EN 12177) and vapour lock index (PN-EN 228)

Key parameters

Standard

Standard number

PN-EN 13132:2005 (wersja polska; EN 13132:2000 IDT)

Title (PL)

Ciekłe przetwory naftowe — Benzyna bezołowiowa — Oznaczanie tlenowych związków organicznych i całkowitej zawartości organicznie związanego tlenu metodą chromatografii gazowej z przełączaniem kolumny

Title (EN)

Liquid petroleum products — Unleaded petrol — Determination of organic oxygenate compounds and total organically bound oxygen content by gas chromatography using column switching

Step-by-step procedure

1. Sampling

   According to EN ISO 3170 or EN ISO 3171 or national regulations, unless otherwise specified in the commodity specification. PN-EN 13132:2005 current (PKN catalogue card as of 03.10.2026).

2. Setting up the chromatograph

   Set up the apparatus according to the manufacturer’s instructions; adjust carrier gas pressure and flow so that the resolution after the second column is at least 1.

3. Calibration

   Calibration sample of weighed oxygenates and internal standard, diluted with oxygenate-free petrol or n-heptane; record retention times and calculate fi for each component.

4. Density

   Determine the density of the sample at 15 °C according to EN ISO 3675, 3838 or 12185 to 0,1 kg/m³.

5. Test sample preparation

   Cool to 5–10 °C; weigh the container with septum, add the internal standard (2–5 % (m/m), ≥ 0,050 g), weigh, add 5–100 ml of sample, seal immediately, weigh (0,1 mg) and mix.

6. Analysis

   Inject a quantity that does not exceed the column capacity or detector linearity; identify the components by retention times.

7. Calculation

   mi = Ai · fi · mst / Ast; ωi = mi / ms · 100 in % (m/m); φi = Vi / Vs · 100 in % (V/V) from the densities of the components (Annex A) and of the sample.

Required equipment and apparatus

Reagents, media and consumables

Health and safety (OHS)

• Hydrogen mixed with air is explosive at concentrations from about 4 % to 75 % (V/V) — joints and lines carrying hydrogen shall be gas tight so that hydrogen does not accumulate in a confined space (4.1)
• Use of the standard can involve hazardous materials, operations and equipment; the standard does not address all hazards, and safety practices are established by the user (warning in Clause 1)

Frequently asked questions