Measuring Hydrocarbon Oil Index
according to ISO 9377-2 (DIN H53)
Abstract
Agilent Technologies developed this ana-
lytical method to comply with ISO 9377-2
and DIN H53 Standards. The method
employs a simple instrument configuration
consisting of a Gas Chromatograph (GC)
equipped with a Split/Splitless (S/SL) inlet
and Flame Ionisation Detector (FID), making
the method both easy to implement and
robust to operate. The combination of an
Agilent GC system (see configuration
above), selected capillary GC column,
proprietary injection port liner, appropriate
chemical standards as well as method
installation and support by an Agilent
Applications Specialist, provide a complete
solution for the measurement of the
Hydrocarbon Oil Index.
Environmental Application
Gas Chromatography
Bernhard Wst
Introduction considerations resulted in the change to a
non-polar solvent for HOI determinations.
The Hydrocarbon Oil Index (HOI) is defined
as the total amount of compounds which This analytical method complies with the
can be extracted from the sample (potable ISO Standard 9377-2 for the determination
water, surface water and waste water) of the Hydrocarbon Oil Index by Gas
with a non-polar solvent having a boiling Chromatography. The method is suitable for
point between 39C and 69C (replacing HOI determinations in concentrations above
the use of halogenated solvents). In 0.1 mg/L in drinking waters, surface waters,
addition, the compounds must not absorb on waste waters and waters from sewage
Florisil and must elute between n-decane treatment plants.
(C10H24) and n-tetracontane (C40H82)
when analysed by GC using an apolar
analytical column. Restrictions on the use of
halogenated hydrocarbons as solvents for
analytical applications combined with the
increasing cost of and reduced availability of
technical grade halogenated solvents as well
as documented environmental
Publication number 5988-0621EN Agilent Technologies Page 2

Experimental Instrument Parameters

The Agilent 6890 and Agilent 6850 Gas Oven temperature Isothermal 35C (1.5 min), ramp 5C/min to 60C hold 0 min,
Chromatographs are well suited to the HOI profile ramp 15C/min to 350C hold 5 min.
application. Both instruments use the same Inlet (S/SL) 375C Splitless Mode
Split/Splitless inlet system and identical Detector (FID) 375C
Flame Ionisation Detector. Discrimination Analytical Column Agilent Part Number 19095Z-221E (HP1, 15m x 0.53mm x 0,15 m)
effects on higher boiling compounds are the Inlet Liner Agilent Part Number 5183-4647
most critical aspect of the analysis and are Carrier Gas Helium
prevented by the use of a special injection Carrier Gas 7.4 ml/min Constant Flow Mode
port liner which, in combination with the Flow Rate
Agilent S/SL inlet system, produces robust Injection Mode Automated (Agilent 7683) Fast Injection
and reliable data. Additional benefits such Injection Volume 1.0 l
as reduced maintenance time and faster
analytical cycle times are also available by
using a S/SL inlet as compared to a Cool-on- Calibration Curve
Column inlet. Hydrocarbon
Hydrocarbon
Index, A Index, FID1 A
FID1

The Agilent GC ChemStation standard Area Area = -375.37592

20647.3902*Amt-375.37592
20647.3902*Amt
=
Area
Area Rel. Res%(7):-4.0289e-1
software is able to subtract background
Rel.
Res%(7):
-4.0289e-1

signals to produce a chromatogram with 40000

7

any column bleed removed. In addition, both 35000

the Agilent 6890 and 6850 are able to save 30000

column compensation signals in memory

25000
and subsequently subtract the column 6

background from the sample data and 20000

5

provide a background-subtracted signal to 15000

4

the ChemStation or data integration 10000 3

system. Standard ChemStation software 5000 2

tools are used to control the GC and 1
Correlation:
0.99918 0.99918
perform the data analysis required of the
0 Correlation:

Amount
Amount[mg[mq/m]
sample data. A custom report template is
0 0.5 1 1.5 /m]l

included with the HOI method and

Figure 1: Oil Standards Calibration Curve
generates a report conforming to the ISO
Standard (see figure 3).

FID1 A, (HYC2509\007F0702.D)
4.207

pA
90
22.535

80

70
13.331

60

50

40

30
2.6012.513

20
3.494 3.377
3.647
2.045
2.158

3.128
2.783
3.011
2.250

22.641
4.103

10

5 10 15 20 25 30 min

Figure 2: 0.6 mg/ml Oil Standard

Publication number 5988-0621EN Agilent Technologies Page 3

Discrimination Test: 150.0

25 sequential injections of a standard 140.0

containing tetracontane C-40 and decane

C-10 were run to test for discrimination
130.0

effects within the analytical system. The 120.0

data obtained is presented in Figure 3 and 110.0

demonstrates the robustness of the method 100.0

and that the analytical system clearly

passes the discrimination test specified in 90.0

the ISO Standard. 80.0

70.0

Results and Dicussion 60.0

The Agilent 6890 and 6850 Gas

50.0
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0 18.0 19.0 20.0 21.0 22.0 23.0 24.0

A mount / Run No. [Decane C10] A mount / Run No. [Tetrac ontane C40] Amount ( Mean ) A mount ( Mean )

Chromatographs equipped with a

Split/Splitless inlet and Flame Ionisation Figure 3: Discrimination Test
Detector can be used for Hydrocarbon Oil
Index determinations in accordance with ISO Data file : C:\HPCHEM\1\DATA\HYC2509\008F0802.D
Sample Name : 1000 mg/l 1
9377-2 (DIN H53) standard. In addition, the ===================================================================
Injection Date : 9/26/2000 3:23:50 AM Seq Line : 8
analytical system is easy to operate and Sample Name
Acq Operator
: 1.0 mg/ml
: berwuest
Vial No. : 8
Inj. No. : 2
requires minimal maintenance. Together, the Inj. Vol. : -
Agilent GC, analytical capillary column, Acq.Method
Analysis Method
: HYCA04.M
: C:\HPCHEM\1\METHODS\ISO93774.M
special inlet liner, custom report template, Last Changed : Fri, 29. Sep. 2000, 10:04:10 am

selected chemical standards and Agilent Analysis of Hydrocarbon Index according to Iso 9377-4 and
DIN H53
applications expertise provide a complete
analytical solution for Hydrocarbon Oil Index
FID1 A, (HYC2509\008F0802.D)
13.332

pA
4.207

determinations. 80

70
22.533

60

50

40

30
2.512

3.645

20
2.156

3.378
3.2543.127
2.599
2.044

3.009
2.781
3.492
2.248

4.101

10

5 10 15 20 30
25 min

============================================================================
Hydrocarbon Index Report
============================================================================
Calib. Data Modified : Fri, 29. Sep. 2000,08:25:56 am
Multiplier : 1.000000

Hydrocarbon Index 1.052 mg/ml

Low Boilers 9.061 mg/l
High Boilers not detectable mg/l

============================================================================
Detailed Report
============================================================================
Name StartTime EndTime Ret Time Total Area Res.F Amount
----------------------------------------------------------------------------
Low Boilers 2.00 4.00 - 239.48 0.03784 9.06
Decane C10 - - 4.21 213.73 0.03784 8.09
Hydrocarbon Index 4.31 22.37 13.33 15408.08 0.00006 1.05
Tetracontane C40 - - 22.53 205.67 0.03247 7.94
High Boilers - - - - - n.d.
============================================================================

Figure 4: Report Printout

Bernhard Wst is an application chemist
based at
Agilent Technologies GmbH
Hewlett Packard Str. 8
76337 Waldbronn
Germany

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Publication Number 5988-0621EN