An American National Standard

Designation: D 5442 – 93 (Reapproved 2003)e1

Standard Test Method for

Analysis of Petroleum Waxes by Gas Chromatography1
This standard is issued under the fixed designation D 5442; 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 (e) indicates an editorial change since the last revision or reapproval.

e1 NOTE—Warning notes were editorially moved into the standard text in August 2003.

1. Scope E 260 Practice for Packed Column Gas Chromatography5

1.1 This test method covers the quantitative determination E 355 Practice for Gas Chromatography Terms and Rela-
of the carbon number distribution of petroleum waxes in the tionships5
range from n-C17 through n-C44 by gas chromatography using
3. Terminology
internal standardization. In addition, the content of normal and
non-normal hydrocarbons for each carbon number is also 3.1 Definitions of Terms Specific to This Standard:
determined. Material with a carbon number above n-C44 is 3.1.1 carbon number—a number corresponding to the num-
determined by its difference from 100 mass % and reported as ber of carbon atoms in a hydrocarbon.
C45+. 3.1.2 cool on-column injection—a sample introduction
1.2 This test method is applicable to petroleum derived technique in gas chromatography where the sample is injected
waxes, including blends of waxes. This test method is not inside the front portion of a partition column at a temperature
applicable to oxygenated waxes, such as synthetic polyethyl- at or below the boiling point of the most volatile component in
ene glycols (for example, Carbowax2), or natural products such the sample.
as beeswax or carnauba. 3.1.3 low volume connector—a metal or glass union de-
1.3 This test method is not directly applicable to waxes with signed to connect two lengths of capillary tubing. Usually
oil content greater than 10 % as determined by Test Method designed so that the tubing ends are joined with a minimum of
D 721. either dead volume or overlap between them.
1.4 The values stated in SI units are to be regarded as the 3.1.4 non(normal paraffın)hydrocarbon (NON)—all other
standard. hydrocarbon types excluding those hydrocarbons with carbon
1.5 This standard does not purport to address all of the atoms in a single length. Includes aromatics, naphthenes, and
safety concerns, if any, associated with its use. It is the branched hydrocarbon types.
responsibility of the user of this standard to consult and 3.1.5 normal paraffın—a saturated hydrocarbon which has
establish appropriate safety and health practices and deter- all carbon atoms bonded in a single length, without branching
mine the applicability of regulatory limitations prior to use. or hydrocarbon rings.
3.1.6 wall coated open tube (WCOT)—a term used to
2. Referenced Documents specify capillary columns in which the stationary phase is
2.1 ASTM Standards: coated on the interior surface of the glass or fused silica tube.
D 721 Test Method for Oil Content of Petroleum Waxes3 Stationary phase may be cross-linked or bonded after coating.
D 4307 Practice for Preparation of Liquid Blends for Use as
4. Summary of Test Method
Analytical Standards4
D 4419 Test Method for Determination of Transition Tem- 4.1 Weighed quantities of the petroleum wax and an internal
peratures of Petroleum Waxes by Differential Scanning standard are completely dissolved in an appropriate solvent and
Calorimetry (DSC)4 introduced into a gas chromatographic column that separates
D 4626 Practice for Calculation of Gas Chromatographic the hydrocarbon components by increasing carbon number.
Response Factors4 The column temperature is linearly increased at a reproducible
rate until the sample is completely eluted from the column.
4.2 The eluted components are detected by a flame ioniza-
1
This test method is under the jurisdiction of ASTM Committee D02 on tion detector and recorded on a strip chart or computer system.
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
D02.04 on Hydrocarbon Analysis. The individual carbon numbers are identified by comparing the
Current edition approved May 10, 2003. Published August 2003. Originally retention times obtained from a qualitative standard with the
approved in 1993. Last previous edition approved in 1998 as D 5442–93 (1998).
2
Carbowax is a registered trademark of Union Carbide Corp.
3
Annual Book of ASTM Standards, Vol 05.01.
4 5
Annual Book of ASTM Standards, Vol 05.02. Annual Book of ASTM Standards, Vol 03.06.

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

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 D 5442 – 93 (2003)e1
retention times of the wax sample. The percent of each 6.2.1 Care must be taken that the sample size chosen does
hydrocarbon number through C44 is calculated via internal not allow some peaks to exceed the linear range of the detector
standard calculations after applying response factors. or overload the capacity of the column.
4.3 For samples with final boiling points greater than 538°C 6.3 Column(s)—Any column used must meet the chromato-
complete elution of all components may not be achieved under graphic resolution specification in 9.5. WCOT columns with 25
the specified conditions. For this reason, the C45+ material is to 30-m lengths and a stationary phase coating of methyl
determined by summing the concentrations of each individual siloxane or 5 % phenyl methyl siloxane have been successfully
carbon number through C44 and subtracting this total from 100 used. Cross-linked or bonded stationary phases are preferred.
mass %. 6.4 Recorder—A recording potentiometer or equivalent
with a full-scale deflection of 5 mV or less for measuring the
5. Significance and Use detector signal versus time. Full scale response time should be
5.1 The determination of the carbon number distribution of 2 s or less. Sensitivity and stability should be sufficient to
petroleum waxes and the normal and non-normal hydrocarbons generate greater than 2-mm recorder deflection for a hydrocar-
in each can be used for control of production processes as well bon injection of 0.05 mass % under the analysis conditions
as a guide to performance in many end uses. employed.
5.2 Data resulting from this test method are particularly 6.5 Integrator or Computer—Means must be provided for
useful in evaluating petroleum waxes for use in rubber formu- integrating the detector signal and summing the peak areas
lations. between specific time intervals. Peak areas can be measured by
computer or electronic integration. The computer, integrator, or
6. Apparatus gas chromatograph must have the capability of subtracting the
6.1 Chromatograph—Any gas chromatographic instrument area corresponding to the baseline (blank) from the sample
that can accommodate a WCOT column, equipped with a flame area, and have the ability to draw the baselines used for peak
ionization detector (FID), and that can be operated at the area integration.
conditions given in Table 1 may be employed. The chromato-
graph should be equipped with a cool on-column inlet (or 7. Reagents and Materials
equivalent) for introducing appropriate quantities of sample 7.1 Carrier Gas—Carrier gas appropriate for the flame
without fractionation. In addition, the gas chromatograph must ionization detector. Hydrogen and helium have been used
be capable of generating a chromatogram where the retention successfully. The minimum purity of the carrier gas used
times of an individual peak have retention time repeatability should be 99.95 mol %. (Warning—Hydrogen and helium are
within 0.1 min. Refer to Practices E 260 and E 355 for general compressed gases under high pressure. Hydrogen is an ex-
information on gas chromatography. tremely flammable gas.)
6.2 Sample Introduction System—Any system capable of 7.2 n-hexadecane—Hydrocarbon to be added to samples as
introducing a representative sample onto the front portion of a an internal standard. Minimum purity of 98 % is required.
WCOT column may be employed. Cool on-column injection is 7.3 Standards for Calibration and Identification—Standard
preferred, however other injection techniques can be used samples of normal paraffins covering the carbon number range
provided the system meets the specification for linearity of (through C44) of the sample are needed for establishing the
response in 9.6. For cool on-column injection, syringes with retention times of the individual paraffins and for calibration
0.15 to 0.25-mm outside diameter needles have been used for quantitative measurements. Hydrocarbons used for stan-
successfully for columns 0.25-mm inside diameter or larger dards must be greater than 95 % purity.
and standard 0.47-mm outside diameter syringe needles have 7.4 Solvent—A liquid (99 % pure) suitable for preparing a
been used for columns 0.53-mm inside diameter or greater. quantitative mixture of hydrocarbons and for dissolving petro-
leum wax. Cyclohexane has been used successfully.
(Warning—Solvents are flammable and harmful if inhaled.)
TABLE 1 Typical Operating Conditions 7.5 Linearity Standard—Prepare a weighed mixture of
Column length (m): 25 30 15 n-paraffins covering the range between n-C16 to n-C44 and
Column inside 0.32 0.53 0.25
diameter (mm):
dissolve the mixture in cyclohexane. Use approximately equal
Stationary phase: DB-1 RTX-1 DB-5 amounts of each of the paraffins and a balance capable of
methyl silicone methyl silicone 5 % phenyl methyl determining mass to within 1 % of the mass of each compound
silicone
Film thickness (µm): 0.25 0.25 0.25
added. It is not necessary to include every n-paraffin in this
Carrier gas: Helium Helium Helium mixture so long as the sample contains n-C16, n-C44, and at
Carrier flow (mL/min): 1.56 5.0 2.3 least one of every fourth n-paraffin. It will be necessary to
Linear velocity (cm/s): 33 35 60
Column initial 80 80 80
prepare the standard sample in cyclohexane, so that the normal
temperature (°C): paraffins are completely dissolved in the solvent. Solutions of
Program rate (°C/min): 10 8 5 0.01 mass % n-paraffin have been used successfully. This
Final temperature (°C): 380 340 350
Injection technique: cool on-column cool on-column cool on-column
sample must be capped tightly, to prevent solvent loss which
Detector temperature 380 400 375 will change the concentration of paraffins in the standard blend.
(°C):
Sample size (µL): 1.0 1.0 1.0 NOTE 1—Refer to Practice D 4307 for details of how to prepare
hydrocarbon mixtures.

2
 D 5442 – 93 (2003)e1
7.6 Internal Standard Solution—Prepare a dilute solution of 9.3 Baseline Blank—After conditions have been set to meet
internal standard in cyclohexane in two steps as follows: performance requirements, program the column temperature
7.6.1 Prepare a stock solution containing 0.5 mass % n-C16 upward to the maximum temperature to be used. Once the
in cyclohexane by accurately weighing approximately 0.4 g column oven temperature has reached the maximum tempera-
n-C16 into a 100 mL volumetric flask. Add 100 mL of ture, cool the column to the selected starting temperature.
cyclohexane and reweigh. Record the mass of n-C16 to within Without injecting a sample, start the column temperature
0.001 g and the mass of solution (cyclohexane and n-C16) to program, the recording device and the integrator. Make two
within 0.l g. baseline blank runs to determine if the baseline blank is
7.6.2 Prepare a dilute solution of n-C16 internal standard by repeatable. If the detector signal is not stable or if the baseline
diluting one part of stock solution with 99 parts of cyclohex- blanks are not repeatable, then the column should either be
ane. Calculate the concentration of internal standard in the conditioned further or replaced.
dilute solution using Eq 1. 9.3.1 Baseline Bleed—Observe the detector response from
WISTD 100 % the blank run on the recorder. Some increase in detector
CISTD 5 W 3 100 (1)
S response will be observed at the upper column temperatures
due to stationary phase bleed. Column bleed is acceptable so
where:
long as the duplicate baseline blank analyses are repeatable.
CISTD = mass % n-C16 internal standard in dilute solu-
The baseline should be a smooth curve, free of any chromato-
tion,
WISTD = weight of n-C16 from 7.6.1, graphic peaks.
Ws = weight of cyclohexane plus n-C16 from 7.6.1, 9.4 Solvent Blank—Make a 1-µL injection of the cyclohex-
100 % = factor to convert weight fraction to mass %, and ane solvent and program the column oven. The solvent is of
100 = dilution factor. suitable purity if there are no detected peaks within the
retention time range over which the wax samples elute.
8. Sampling 9.5 Column Resolution—Check the efficiency of the GC
8.1 To ensure homogeneity, completely mix the entire wax column by analyzing, under conditions specified in 10.2, a
sample by heating it to 10°C above the temperature at which 1-µL injection of 0.05 mass % solution of n-C20 and n-C24 in
the wax is completely molten and then mix well by stirring. cyclohexane. The column resolution must not be less than 30 as
Using a clean eyedropper, transfer a few drops to the surface of calculated using Eq 2.
a clean sheet of aluminum foil, allow to solidify and break into 2d
pieces. The wax can either be used directly as described in R5 (2)
1.699~W1 1 W2!
Section 11 or placed in a sealed sample vial until ready for use.
8.1.1 Aluminum foil usually contains a thin film of oil from where:
processing. This oil must be removed by rinsing the foil with d = distance (mm) between the peak maxima of n-C20
solvent such as hexane or mineral spirits, prior to use. and n-C24,
W1 = peak width (mm) at half height of n-C20, and
W2 = peak width (mm) at half height of n-C24.
9. Preparation of Apparatus
9.6 Linearity of Response—For quantitative accuracy, de-
9.1 Column Conditioning—Capillary columns with bonded tector response must be proportional to the mass of hydrocar-
(or cross-linked) stationary phases do not normally need to be bon injected, and the response of the non-normal paraffins is
conditioned; however, it is good chromatographic practice to assumed to be equivalent to the response of the n-paraffin with
briefly condition a new column as described below. the same carbon number. In addition, sample injection tech-
9.1.1 Install the column in the chromatographic oven and nique and sample solution properties must be such that
connect one column end to the sample inlet system. Turn on the representative sample is introduced to the gas chromatograph
source of carrier gas and set the flow controller (or pressure without discrimination. Before use, the analysis system must
regulator) to the flow rate to be used in the analysis. Increase be shown to conform to these requirements as specified in
the column temperature to the maximum value to be used in the 9.6.1.
analysis and maintain this temperature for 30 min. Cool the
column temperature to room temperature and connect the 9.6.1 Analyze the linearity standard described in 7.5 and
remaining column end to the detector. Care must be taken that calculate the relative mass response factors according to
the column terminates as close as possible to the tip of the FID Practice D 4626. Response factors calculated relative to hexa-
jet. The temperature of the column between the column oven decane must be between 0.90 and 1.10.
and the detector jet must be maintained above the maximum 9.6.2 If relative response factors are not within the limits
column temperature. stated above, take appropriate action and reanalyze the linear-
9.2 Operating Conditions—Set the chromatographic oper- ity standard to ensure linearity and the absence of discrimina-
ating conditions (see Table 1) and allow the system to achieve tion.
all temperature setpoints. The recorder, computer or integrating 9.7 Retention Time Repeatability—Check the retention time
device should be connected so that a plot of the detector signal repeatability by analyzing the linearity standard in duplicate.
versus time can be obtained. Make certain that the FID is Retention times for duplicate analyses must not differ by more
ignited before proceeding. than 0.10 min between duplicate runs.

3
 D 5442 – 93 (2003)e1
10. Calibration and Standardization NOTE 2—Some commercially available gas chromatographs have soft-
ware routines as part of their standard systems to make the baseline
10.1 n-Paraffın Identification—Determine the retention
correction directly to the detector signal. With such systems, no computer
time of each n-paraffin in the range from C16 to C44 by subtraction of the blank is necessary.
injecting small amounts of each paraffin either separately or in
known mixtures. Completely dissolve samples in cyclohexane. 11.3 Following the same procedure as for the blank run (see
10.2 Standardization—Inject the linearity standard de- 11.2), inject 0.5 to 1.0 µL of the wax sample solution from 11.1
scribed in 7.5 and measure the peak area of each n-paraffin by into the cool on-column injection port. Immediately start the
electronic integrator or computer. temperature program, the recorder, and the integrator, and store
10.2.1 Calculate the response per unit mass of the detector the acquired detector signal.
for each component in the linearity standard, relative to n-C16, 11.4 Integrate the stored detector signal twice, using the
according to Practice D 4626. baseline construction parameters as directed below.
11. Procedure 11.4.1 Using a valley to valley baseline construction, inte-
11.1 Prepare a solution of the petroleum wax sample for grate the detector signal to obtain an area (see Fig. 1) for each
analysis as follows: peak in the chromatogram. Based on the retention times
11.1.1 Obtain a petroleum wax sample specimen as directed determined in 10.1, identify the normal paraffin peaks and
in 8.1. tabulate only their areas. Also record the area of the
11.1.2 Accurately weigh about 0.0100 g of the wax speci- n-C16(hexadecane) internal standard peak that must be com-
men into a glass vial of approximately 15-mL capacity. Add pletely resolved (baseline separation) from the wax sample
approximately 12 mL of the dilute internal standard solution area.
(0.005 mass % n-C16 in cyclohexane), cap the vial and 11.4.2 Using a vertical drop to a horizontal baseline con-
determine the exact weight of dilute internal standard solution struction (see Fig. 2, Fig. 3), integrate the detector signal a
added. Record both weights. second time. Sum the area of all the peaks of each carbon
11.1.3 Agitate the vial until the wax is dissolved, using number and tabulate these totals. By convention, the peaks
gentle heating if necessary. assigned the carbon number n are those that elute between the
11.1.4 For manual syringe injections, fill the syringe directly valley immediately following the normal paraffin peak (Cn-1)
from this vial. For automatic syringe injections, transfer a and the corresponding valley following the next normal paraf-
suitable aliquot to the appropriate autosampler vial. fin peak (Cn).
11.2 Before analyzing wax samples, program the column 11.4.3 To ensure proper and consistent integrations, plot the
temperature to the maximum temperature used. Once the chromatogram with drawn in baseline after each integration
column temperature has reached the maximum, cool the
and confirm that the baselines match Fig. 1 and Fig. 2.
column to the selected starting temperature, and allow it to
equilibrate at this temperature for at least 3 min. Without 11.4.4 Do not include, as part of the sample, any peaks
injecting any material, initiate a blank run by starting the resulting from the solvent or the internal standard.
temperature program, recorder, and integrator and allow to NOTE 3—The total area for each carbon number can be measured by
continue until at least 2 min after the retention time of n-C44. either pre-programming the integrator to sum the area of the peaks within
Store a record of this blank run in the computer or integration the appropriate retention time windows or by analyzing the peak area data
device for subtraction from the sample area. after the peak integration process is complete.

FIG. 1 Valley to Valley Integration for Area of Normal Paraffin

4
 D 5442 – 93 (2003)e1

FIG. 2 Carbon Number Summation (Vertical Drop to Horizontal Baseline)

FIG. 3 Typical Wax Chromatogram

12. Calculation sample = weight of wax sample, and

12.1 Each Carbon Number—Calculate the mass % for each CISTD = mass % of n-C16 in internal standard mixture.
carbon number determined in 11.4.2 using Eq 3.
Areai MIX
12.2 Normal Paraffın—Calculate the mass % of each nor-
Ci 5 Area 3 RRFi 3 sample 3 CISTD (3) mal paraffin hydrocarbon from the individual areas determined
ISTD
in 11.4.1 using Eq 4.
Areai MIX
where: Ni 5 Area 3 RRFi 3 sample 3 CISTD (4)
ISTD
Ci = mass % of hydrocarbons with carbon number
i,
areai = area sum of hydrocarbons with carbon number where:
i, Ni = mass % of normal paraffin with carbon num-
areaISTD = area of n-C16 internal standard peak, ber i,
RRFi = response factor, relative to n-C16, areai = peak area of normal paraffin with carbon
MIX = weight of dilute internal standard/solvent mix- number i,
ture, areaISTD = area of n-C16 internal standard peak,

5
 D 5442 – 93 (2003)e1

RRFi = response factor, relative to n-C16, where:

MIX = weight of dilute internal standard/solvent mix- (Ci = the sum of the mass % of all detected hydrocarbons.
ture,
sample = weight of wax sample, and
CISTD = mass % of n-C16 in internal standard mixture. 13. Report
13.1 Report the concentration in mass percent of the normal
12.3 Non-Normal Paraffın Hydrocarbon—The non-normal (Ni) and non-normal (NONi) hydrocarbons for each carbon
paraffin hydrocarbons are calculated as the difference between number in the sample to the nearest 0.01 mass percent. Report
the mass percent of hydrocarbons with carbon number i (Ci) also the amount of residual as % C45+.
and the mass percent of the n-paraffin with carbon number i
(Ni): 14. Precision and Bias 6
NONi 5 Ci 2 Ni (5) 14.1 Precision—The precision of this test method as deter-
where: mined by statistical examination of interlaboratory test results
NON(i) = mass percent of the non-normal paraffin hydro- is as follows:
carbons of each carbon number. 14.1.1 Repeatability—The difference between the two test
12.3.1 The response for all components in a carbon number results, obtained by the same operator with the same apparatus
is assumed to be the same as the response for the normal under constant operating conditions on identical test material,
paraffin of the same carbon number as determined in 10.2. would, in the long run, in the normal and correct operation of
the test method, exceed the values in Table 2 only in one case
12.3.2 Relative response factors for individual n-paraffins
in twenty.
between those determined from the calibration mixture are
14.1.2 Reproducibility—The difference between two single
obtained by interpolation.
and independent results, obtained by different operators work-
12.4 Calculate the mass percent Of C45+ according to Eq 6: ing in different laboratories on identical test materials would, in
mass % C451 5 100 % 2 (Ci (6) the long run, in the normal and correct operation of the test
method, exceed the values in Table 2 only in one case in
twenty.
TABLE 2 Repeatability and Reproducibility 14.2 Bias—Bias cannot be determined because there is no
Carbon Number Range, mass % RepeatabilityA RepeatabilityA reference material suitable for determining the bias of the
C21 0.11–0.25 0.014 0.039 procedure in this test method.
C23 0.04–2.90 0.0463 X0.30 0.1663 X0.30
C26 0.01–8.94 0.0785 X0.56 0.4557 X0.56 15. Keywords
C29 0.04–8.15 0.0872 X0.31 0.3984 X0.62
C32 0.44–5.05 0.1038 X0.50 0.6472 X0.50 15.1 gas chromatography; non-normal paraffin hydrocar-
C35 2.52–5.62 0.1737 X 0.4540 X
C38 0.44–3.61 0.1131 0.5476 (X + 0.1069)
bons; normal paraffin; paraffin wax; petroleum wax
(X + 0.1069)
C41 0.06–2.96 0.1600 X 0.5460 X
C44 0.02–2.26 0.4990 X0.60 0.9220 X0.60
Total n-paraffins 18.73–79.52 2.64 26.03 6
Supporting data have been filed at ASTM International Headquarters and may
A
Where X is the mass % of the component. be obtained by requesting Research Report RR:D02-1316.

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