C8 and Lower Boiling Paraffins and Naphthenes

in Low-Olefin Hydrocarbons by GC
UOP Method 690-13
Scope
This gas chromatographic method is for determining C8 and lower boiling paraffins and naphthenes
in hydrocarbons containing less than 2 mass-% olefins (see Note 1) having a maximum final boiling
point of 260°C. Benzene and toluene are also determined. Certain non-aromatic components of
interest are reported as composites and C8 aromatics are not determined (see Note 2). The
quantitation limit for any reported component is 0.01 mass-%.

References
ASTM Method D4307, “Preparation of Liquid Blends for Use as Analytical Standards,”
www.astm.org
ASTM Method D6839, “Hydrocarbon Types, Oxygenated Compounds, and Benzene in Spark
Ignition Engine Fuels by Gas Chromatography,” www.astm.org
Scanlon, J. T. and Willis, D. E., Journal of Chromatographic Science, 23, 333-340 (1985)
UOP Method 304, “Bromine Number and Bromine Index of Hydrocarbons by Potentiometric
Titration,” www.astm.org
UOP Method 744, “Aromatics in Hydrocarbons by GC,” www.astm.org

Outline of Method
Two gas chromatographic analyses using the same column are required to determine the greatest
number of resolved non-aromatic components. Based on the degree of resolution required, either
Analysis A alone, or both Analyses A and B may be used. In both analyses, a sample is injected into
a gas chromatograph that is equipped with a fused silica capillary column and a flame ionization
detector (FID). A separate set of operating conditions is used for each analysis. The mass-%
composition of the sample is obtained by the internal normalization technique of quantitation,
wherein component peak areas for the entire sample are first corrected for differences in response and
then normalized to 100%. Some unresolved non-aromatic components from Analysis A can then be
resolved and calculated using data obtained from Analysis B (see Note 3).

IT IS THE USER'S RESPONSIBILITY TO ESTABLISH APPROPRIATE PRECAUTIONARY PRACTICES AND TO

DETERMINE THE APPLICABILITY OF REGULATORY LIMITATIONS PRIOR TO USE. EFFECTIVE HEALTH AND
SAFETY PRACTICES ARE TO BE FOLLOWED WHEN UTILIZING THIS PROCEDURE. FAILURE TO UTILIZE THIS
PROCEDURE IN THE MANNER PRESCRIBED HEREIN CAN BE HAZARDOUS. SAFETY DATA SHEETS (SDS) OR
EXPERIMENTAL SAFETY DATA SHEETS (ESDS) FOR ALL OF THE MATERIALS USED IN THIS PROCEDURE SHOULD
BE REVIEWED FOR SELECTION OF THE APPROPRIATE PERSONAL PROTECTION EQUIPMENT (PPE).
© COPYRIGHT 1970, 1973, 1987, 1993, 1999, 2013 UOP LLC. All rights reserved.
Nonconfidential UOP Methods are available from ASTM International, 100 Barr Harbor Drive, P.O. Box C700, West
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 2 of 14

Apparatus
References to catalog numbers and suppliers are included as a convenience to the method user.
Other suppliers may be used.
Balance, readable to 0.0001 g
Chromatographic column, 50 m of 0.20-mm ID fused silica capillary, internally coated to a film
thickness of 0.5-µm with cross-linked methyl silicone, Agilent Technologies, Cat. No. 19091S-
001. Use of this specific column is recommended. The same column is used for Analysis A and
Analysis B.
Data system, or electronic integrator, for obtaining peak areas. This device must integrate areas at a
sufficiently fast rate so that narrow peaks typically resulting from use of a capillary column can
be accurately measured. Agilent Technologies, ChemStation
Gas chromatograph, capable of multiple temperature ramping and capable of cryogenic operation
at 32°C, built for capillary column chromatography utilizing a split injection system, having a
glass injection port insert, and equipped with a flame ionization detector that will give a
minimum peak height response of 5 times the background noise for 0.01 mass-% of benzene
when operated at the recommended conditions. Electronic pressure control (EPC) is
recommended. Agilent Technologies, Model 7890
Gas purifier, to remove oxygen from the hydrogen carrier gas, VICI Mat/Sen, Cat. No. P-200-1
Leak detector, gas, Grace Davison, Cat. No. 21-250
Refrigerator, explosion-proof or flammable storage, VWR, Cat. No. 55700-340
Regulator, air, two-stage, high purity, delivery pressure range 30-700 kPa (4-100 psi), Matheson
Tri-Gas, Model 3122-590
Regulator, hydrogen, two-stage, high purity, delivery pressure range 30-700 kPa (4-100 psi),
Matheson Tri-Gas, Model 3122-350
Regulator, nitrogen, two-stage, high purity, delivery pressure range 30-700 kPa (4-100 psi),
Matheson Tri-Gas, Model 3122-580
Sample injector, any syringe or injector capable of injecting a 0.5-µL volume of sample. An
automatic injection device is recommended. Agilent Technologies, Model 7683

Reagents and Materials

References to catalog numbers and suppliers are included as a convenience to the method user.
Other suppliers may be used.
Air, zero gas, total hydrocarbons less than 2.0 ppm as methane
Benzene, 99.9% minimum purity, Sigma-Aldrich, Cat. No. 270709
Carbon dioxide, liquid, if necessary for cryogenic cooling of the GC column oven to 32°C
n-Hexane, 99% minimum purity, Sigma-Aldrich Chemical, Cat. No. 139386
Hydrogen, zero gas, 99.95% minimum purity, total hydrocarbons less than 0.5 ppm as methane
Nitrogen, zero gas, 99.99% minimum purity, total hydrocarbons less than 0.5 ppm as methane
Syringe, for sample injector, 10-µL, Agilent Technologies, Cat. No. 5181-1273
Toluene, 99% minimum purity, Sigma-Aldrich, Cat. No. 179965
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p-Xylene, 99% minimum purity, Sigma-Aldrich, Cat. No. 134449

Procedure
The analyst is expected to be familiar with general laboratory practices, the technique of gas
chromatography, and the equipment being used. Dispose of used reagents, materials, and samples in
an environmentally safe manner according to local regulations.
Chromatographic Technique
1. Install the gas purifiers in the supply lines between the gas sources and the gas inlets on the gas
chromatograph.
• Column and FID life may be significantly reduced if the gas purifiers are not used.
2. Install the fused silica capillary column in the gas chromatograph.
• CAUTION: Hydrogen carrier gas leakage into a confined volume of the column oven can cause a
violent explosion. It is, therefore, mandatory to test for leaks each time a connection is made and
periodically thereafter.
3. Establish the recommended operating conditions as given in Table 1, Analysis A.
• Other conditions may be used provided they produce the required sensitivity and chromatographic
separations equivalent to those shown in the Typical Chromatogram (Figures 1 and 2).

Table 1
Recommended Operating Conditions
Analysis A Analysis B
Carrier gas hydrogen hydrogen
Column head pressure @ 32°°C 140 kPa (20 psig) 140 kPa (20 psig)
Equivalent flow 1.1 mL/min 1.1 mL/min
Equivalent linear velocity 33 cm/sec 33 cm/sec
Split flow 215 mL/min 215 mL/min
Injection port temperature 230°°C 230°°C
Column temperature program
Initial temperature 32°°C 60°°C
Initial time 6 min 8 min
Programming rate 1 5°°C/min 5°°C/min
Intermediate temperature 52°°C 90°°C
Intermediate time 14 min 0 min
Programming rate 2 20°°C/min 20°°C/min
Final temperature 250°C 250°C
Final time 9 min 10 min
Detector FID FID
Temperature 250°°C 250°°C
Hydrogen flow rate* 30 mL/min 30 mL/min
Air flow rate* 400 mL/min 400 mL/min
Makeup nitrogen flow rate* 30 mL/min 30 mL/min
Sample size 0.5 µL 0.5 µL
*Consult the manufacturer’s instrument manual for suggested flow rates.

4. Program the column oven to 250°C and maintain this temperature until a stable baseline has been
obtained at the required sensitivity.
5. Cool the column oven to 32°C.

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6. Inject 0.5 µL of sample and start the integrator and the column temperature programming
sequence.
• The use of an autoinjector or autosampler automates the injection of the sample into the GC, starts
the data system, and the GC oven program simultaneously.
7. Identify the components by comparing the resultant chromatogram to the Typical Chromatogram
shown in Figures 1 and 2. If necessary, confirm the sites of the aromatic components by
comparison with the calibration blend (see Calibration).
8. Establish the recommended operating conditions as given in Table 1, Analysis B, if resolution of
the co-eluting components in Analysis A is required, and proceed to Steps 9 and 10.
• Other conditions may be used provided they produce the required sensitivity and chromatographic
separations equivalent to those shown in the Typical Chromatogram (Figures 3 and 4).

9. Inject 0.5 µL of sample and start the integrator and the column temperature programming
sequence.
10. Identify the components by comparing the chromatogram obtained to the Typical Chromatogram
shown in Figures 3 and 4. If necessary, confirm the sites of the aromatic components by
comparison with the calibration blend (see Calibration).
Calibration
This analysis uses internal normalization of the entire sample to quantitate the C8 minus
components. In order to accurately analyze the entire sample, C6 through C8 aromatic components
must be identified and response factors determined for them. This is necessary because C6 through C8
aromatic components do not have the same detector response as the non-aromatic components. The
non-aromatic components all have essentially the same detector response. Calibrate whenever
chromatographic conditions have changed and periodically thereafter.
1. Prepare a calibration blend as described in ASTM Method D 4307, “Preparation of Liquid Blends
for Use as Analytical Standards,” to contain approximately equal masses of n-hexane, benzene,
toluene and p-xylene.
• This blend is stable for six months if refrigerated.
2. Analyze the blend in triplicate as described under Chromatographic Technique, Analysis A.
3. Identify the peaks and obtain the peak areas for each component from the triplicate runs.
4. Determine the relative response factor for each component in each run to three decimal places,
using n-hexane as reference and Equation 1.
AB
F= (1)
CD
where:
A= component in the blend, mass-%
B= peak area of n-hexane
C= n-hexane, mass-%
D= peak area of component
F= relative response factor for each component
Relative response factors from each of the triplicate runs should not deviate from the average by
more than 2% of the value. If greater deviations occur, make certain that there are no problems
with the equipment, then make additional runs until the required repeatability is obtained on three
consecutive runs.

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5. Average the relative response factors for each component from the three runs. Use these averages
as J in Equation 2.
Use the relative response factor for n-hexane for all the non-aromatic (see Table 3) and C9+ (the
unidentified peaks eluting after methylcyclohexane in Figure 1) components in the sample. Use the
relative response factor of p-xylene for ethylbenzene, m-xylene, p-xylene and o-xylene.
Calculated relative response factors should be similar to the theoretical relative response factors
shown in Table 2. The theoretical relative response factors were calculated using the effective carbon
number (ECN) concept as described by Scanlon and Willis. If the determined relative response
factors differ by more than 5% from those shown in Table 2, recheck the apparatus, operating
conditions, and blend preparation procedures.
Table 2
Theoretical Relative Response Factors
n-Hexane 1.000
Benzene 0.906
Toluene 0.916
p-Xylene 0.924
If the C9+ components are known to be primarily aromatics, use the response factor for p-xylene
instead of the response factor for n-hexane for the C9+ components.

Calculations
Calculate the concentration of each C8 and lighter component in the sample for Analysis A, and, if
applicable, Analysis B, to the nearest 0.01 mass-% using Eq. 2.
PJ
Component, mass - % = 100 (2)
T
where:
J= average relative response factor of individual component
P= peak area of individual component
T= sum of the products, PJ, of all recorded peaks
100 = factor to convert to mass-%
When Analysis B is used, peaks 30A, 31A, 40A, 40B, 56A, 56B, 56C, 60A, 60B, 62A and 62B (see
Tables 3 and 4) are resolved and the concentrations calculated directly from Analysis B, using
Equations 1 and 2.
Composite peaks 40, 56 and 60, Analysis A, are fully resolved in Analysis B. The Analysis B
individual concentrations require re-normalization to conform to the composite concentration totals in
Analysis A. This is accomplished by use of Equation 3.
WX
Individual component, mass - % = (3)
Y
where:
W = component amount, Analysis B
X = composite amount, Analysis A
Y = sum of component concentrations from Analysis B, in Analysis A composite
Additionally, determine the concentrations for 1-cis-2-dimethylcyclopentane, 2,2-dimethylhexane
and 3-ethylhexane, which are unresolved in Analysis A, from the Analysis A and B data Equations 4,
5, and 6.
1-cis-2-Dimethylcyclopentane, mass-% = L–G (4)
where:
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G = methylcyclohexane, from Analysis B

L = methy1cyclohexane + 1-cis-2-dimethycyclopentane, from Analysis A
2,2-Dimethylhexane, mass-% = N–H (5)
where:
H = 1,1,3-trimethylcyclopentane, from Analysis B
N = 1,1,3-trimethylcyclopentane + 2,2-dimethylhexane, from Analysis A

3-Ethylhexane, mass-% = R–S (6)

where:
R = 3-ethylhexane + l-cis-3-dimethylcyclohexane + 1-cis-2-trans-3-trimethylcyclopentane, from
Analysis A
S = 1-cis-3-dimethylcyclohexane + 1-cis-2-trans-3-trimethylcyclopentane, from Analysis B
If, after all the calculations above, the sum of all components (resolved and unresolved) does not
total 100 mass-%, renormalize the data to 100 mass-%.
Report each component to the nearest 0.01 mass-% below one mass-%, and to three significant
figures at or above one mass-%.
Table 3
Retention Times of
Identified Components, Analysis A
Peak numbers with letter designations refer to co-eluting peaks, i.e.; 30A and
30B co-elute. If some separation of these peaks does occur, it should not be
inferred that A elutes before B.
Typical
Retention Peak
Time, Min No. Component Identification
2.10 * Ethane site
2.35 1 Propane
2.54 2 Isobutane
2.71 3 n-Butane
2.79 4 2,2-Dimethylpropane
3.33 5 Isopentane
3.67 6 n-Pentane
4.32 7 2,2-Dimethylbutane
5.00 8 Cyclopentane
5.04 9 2,3-Dimethylbutane
5.16 10 2-Methylpentane
5.60 11 3-Methylpentane
6.23 12 n-Hexane
7.19 13 2,2-Dimethylpentane
7.28 14 Methylcyclopentane
7.45 15 2,4-Dimethylpentane
7.67 16 2,2,3-Trimethylbutane
8.29 17 Benzene
8.56 18 3,3-Dimethylpentane
8.72 19 Cyclohexane
9.16 20 2-Methylhexane
9.23 21 2,3-Dimethylpentane
9.35 22 1,1-Dimethylcyclopentane
9.58 23 3-Methylhexane
9.86 24 1-cis-3-Dimethylcyclopentane
9.99 25 1-trans-3-Dimethylcyclopentane
10.06 26 3-Ethylpentane

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Typical
Retention Peak
Time, Min No. Component Identification
10.13 27 1-trans-2-Dimethylcyclopentane
10.46 28 2,2,4-Trimethylpentane
10.82 29 n-Heptane
11.93 30A Methylcyclohexane
30B 1-cis-2-Dimethylcyclopentane
12.08 31A 1,1,3-Trimethylcyclopentane
31B 2,2-Dimethylhexane
12.61 32 Ethylcyclopentane
12.70 33 2,5-Dimethylhexane
12.82 34A 2,2,3-Trimethylpentane
34B 2,4-Dimethylhexane
13.20 35 1-trans-2-cis-4-Trimethylcyclopentane
13.30 36 3,3-Dimethylhexane
13.71 37 1-trans-2-cis-3-Trimethylcyclopentane
13.93 38 2,3,4-Trimethylpentane
14.22 39A 2,3,3-Trimethylpentane
39B Toluene
14.78 40A 2,3-Dimethylhexane
40B 1,1,2-Trimethylcyclopentane
14.86 41 2-Methyl-3-ethylpentane
15.29 42 2-Methylheptane
15.41 43 4-Methylheptane
15.53 44A 3,4-Dimethylhexane
44B 3-Methyl-3-ethylpentane
15.74 45A 1-cis-2-trans-4-Trimethylcyclopentane
45B 1-cis-2-cis-4-Trimethylcyclopentane
15.94 46 3-Methylheptane
16.03 47A 3-Ethylhexane
47B 1-cis-3-Dimethylcyclohexane
47C 1-cis-2-trans-3-Trimethylcyclopentane
16.20 48 1-trans-4-Dimethylcyclohexane
16.68 49 1,1-Dimethylcyclohexane
17.03 50 1-Methyl-trans-3-ethylcyclopentane
17.23 51 1-Methyl-cis-3-ethylcyclopentane
17.35 52 1-Methyl-trans-2-ethylcyclopentane
17.56 53 1-Methyl-1-ethylcyclopentane
17.83 54 1-trans-2-Dimethylcyclohexane
18.38 55 1-cis-2-cis-3-Trimethylcyclopentane
18.59 56A n-Octane
56B 1-cis-4-Dimethylcyclohexane
56C 1-trans-3-Dimethylcyclohexane
19.37 57 Isopropylcyclopentane
20.35 58 1-Methyl-cis-2-ethylcyclopentane
21.33 59 1-cis-2-Dimethylcyclohexane
21.92 60A n-Propylcyclopentane
60B Ethylcyclohexane
23.90 61 Ethylbenzene
24.40 62A m-Xylene
62B p-Xylene
25.70 63 o-Xylene

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Table 4
Components Determined by Analysis B
Peak numbers with letter designations refer to co-eluting peaks; i.e., 4A and 4B co-elute.
If some separation of these peaks does occur, it should not be inferred that A elutes before B.

Typical
Retention Peak No., Peak No., Component
Time, Min Analysis B Analysis A Identification
7.05 1A 30B 1-cis-2-Dimethylcyclopentane
1B 31B 2,2-Dimethylhexane
7.12 2 30A Methylcyclohexane
7.17 3 31A 1,1,3-Trimethylcyclopentane
7.51 4A 32 Ethylcyclopentane
4B 34B 2,4-Dimethylhexane
7.66 5 34A 2,2,3-Trimethylpentane
8.74 6 40A 2,3-Dimethylhexane
8.91 7 40B 1,1,2-Trimethylcyclopentane
9.42 8A 47A 3-Ethylhexane
8B 45B 1-cis-2-cis-4-Trimethylcyclopentane
9.59 9A 47B 1-cis-3-Dimethylcyclohexane
9B 47C 1-cis-2-trans-3-Trimethylcyclopentane
10.66 10 56A n-Octane
10.77 11 56B 1-cis-4-Dimethylcyclohexane
10.87 12 56C 1-trans-3-Dimethylcyclohexane
12.02 13 60A n-Propylcyclopentane
12.25 14 60B Ethylcyclohexane

Notes
1. Low concentrations of total olefins may be estimated by summing the unidentified peaks eluting
before methylcyclohexane. Unidentified peaks eluting after methylcyclohexane may include C9
saturates and thus may not be summed for olefin quantitation. If the olefin content so determined
is greater than 2%, interferences will make the paraffin and naphthene results invalid. An
alternative estimate of total olefins may be obtained by analyzing the sample by UOP Method
304, “Bromine Number and Bromine Index of Hydrocarbons by Potentiometric Titration.”
Olefins greater than 2% may also be determined by ASTM Method D 6839, “Hydrocarbon
Types, Oxygenated Compounds, and Benzene in Spark Ignition Engine Fuels by Gas
Chromatography.”
2. Although C8 aromatics are identified and response factors developed, these values may not be as
accurate as other methods specific for aromatics determination due to non-aromatic interference.
Therefore, C8 aromatic values should not be reported from this method. An alternative method
for C8 aromatics is UOP Method 744, “Aromatics in Hydrocarbons by GC.”
3. Analysis A alone is typically sufficient for reformate samples or gasolines having low naphthene
content. For naphthas and gasolines with high naphthene content, both Analyses A and B must
be used.

Precision
Precision statements were determined using UOP Method 999, “Precision Statements in UOP
Methods,” from precision data obtained using an autosampler.

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Repeatability and Site Precision

A nested design was carried out for component analysis with two analysts. Each analyst carried out
tests on two separate days, performing two tests each day using two samples. The total number of
tests performed was 16 for each component. Using a stepwise analysis of variance procedure, the
within-day and within-lab estimated standard deviations (esd) were calculated for the components at
the concentration levels listed in Table 5. Two tests performed by the same analyst on the same day
should not differ by more than the repeatability allowable differences shown in Table 5 with 95%
confidence. Two tests performed in one laboratory by different analysts on different days should not
differ by more than the site precision allowable differences shown in Table 5 with 95% confidence.
The data in Table 5 are a short-term estimate of repeatability. When the test is run routinely, a
control standard and chart should be used to develop a better estimate of the long-term repeatability.
Reproducibility
There is insufficient data to calculate the reproducibility of the test at this time.
Table 5
Repeatability and Site Precision, mass-%
Repeatability Site Precision
Within- Allowable Within- Allowable
Component Mean Day esd Difference Lab esd Difference
Methylcyclopentane 0.22 0.001 0.01 0.001 0.01
Methylcyclopentane 5.64 0.003 0.01 0.019 0.12
Benzene 0.24 0.001 0.01 0.001 0.01
Benzene 9.93 0.005 0.02 0.011 0.07
n-Heptane 1.23 0.001 0.01 0.001 0.01
n-Heptane 7.46 0.003 0.01 0.023 0.14
Methylcyclohexane 0.27 0.001 0.01 0.001 0.01
Methylcyclohexane 7.21 0.004 0.01 0.022 0.04
Toluene 1.38 0.001 0.01 0.001 0.01
Toluene 24.64 0.008 0.03 0.010 0.05

Time for Analysis

The elapsed time for Analysis A only is 0.8 hour with a labor requirement of 0.7 hour. The elapsed
time for both Analyses A and B is 1.6 hours with a labor requirement of 1.3 hours.

Suggested Suppliers
Agilent Technologies, 2850 Centerville Rd., Wilmington, DE 19808-1610, USA, 1-302-633-8000,
www.agilent.com
Grace Davison Discovery Sciences, 2051 Waukegan Rd., Deerfield, IL 60015, USA, 1-847-948-
8600, www.discoverysciences.com
Matheson Tri-Gas, 166 Keystone Dr., Montgomeryville, PA 18936, USA, 1-215-641-2700,
www.mathesontrigas.com
SGE Incorporated, 2007 Kramer Lane, Austin, TX 78758, USA, 1-512-837-7190, www.sge.com
Sigma-Aldrich Co., 1000 West Saint Paul Ave., Milwaukee, WI 53201, USA, 1-414-438-3850,
www.sigma-aldrich.com
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VICI Mat/Sen, 7806 Bobbitt, Houston, TX 77055, USA, 1-713-688-9345, www.vicimatsen.com

VWR International, 1310 Goshen Parkway, West Chester, PA 19380, USA, 1-610-431-1700,
www.vwr.com

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