Consumer Product Propellant Analysis

and an Alternative Standard Blending

Technique for High Concentration
Standards

Application Note

Environmental

Authors Abstract
Wendy Howard An Agilent Technologies gas chromatograph (GC) configured with an automated
California Air Resources Board 6-port gas sample valve, a split injection inlet, an HP-PLOT Q capillary column and a
PO Box 2815 thermal conductivity detector for the analysis of common aerosol propellants:
Sacramento, CA 95812 carbon dioxide (CO2), propane (C3,H8), isobutane (C4H10), n-butane(C4H10),
USA 1,1-difluroethane (HFC-152a), 1,1,1,2-tetrafluroethane (HFC-134a), and dimethyl
ether (C2H6O). Six methods are configured with six different split ratios to allow for
Shannon Coleman
a six point calibration curve for each standard. A method is provided to dynamically
Agilent Technologies, Inc.
dilute samples when a multipoint calibration is desired across a narrow calibration
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range from a single standard.
Santa Clara CA 95051
USA
Introduction dioxide (33%); and Standard 2: propane (25%), n-butane (25%),
isobutane (25%), and dimethyl ether (25%). Standards are diluted
A variety of consumer and industrial products are packaged in across six points using varying split ratios for each method.
self pressurized or aerosol containers. The aerosol propellant
usually consist of a mixture of volatile organic compounds Analysis parameters
(VOCs), which can result in ground level ozone, a smog compo- The GC parameters used in the analysis of propellant are
nent that is detrimental to human health. Products using these shown in Table 2.
propellants can range from spray paints, hairsprays, cleaning
Table 2. Gas Chromatograph
and household products to industrial sealants and lubricants.
About nine billion aerosol units were produced worldwide in GC run conditions
1998. The vast majority of these products were produced by Analytical column HP-PLOT Q, 30 m × 0.53 mm × 40 µm
the United States (three billion) and Europe (four billion). In the Gas sample loop vol 0.1 mL
early 1990s, the United States began to develop a regulation to Inlet temperature 200 °C
limit the VOC content in consumer products. The U.S. Inlet pressure 6.1513 psi
Environmental Protection Agency has now imposed minimum Carrier gas Helium, constant flow mode, 7.0 mL/min
national standards for VOC emissions.[1] Split ratio/flow Method (%) Split ratio Split flow
In this study, we look at a gas chromatography method (mL/min)
5 47.114:1 329.8
for the analysis of some common aerosol propellants:
10 22.843:1 159.9
carbon dioxide (CO2), propane (C3,H8), isobutane (C4H10),
n-butane(C4H10), 1,1-difluroethane (HFC-152a), 20 10.707:1 74.949
1,1,1,2-tetrafluroethane (HFC-134a), and dimethyl ether 50 3.425:1 23.975
(C2H6O). We also demonstrate a method of performing a six 75 1.8:1 12.6
point calibration by using the split inlet as a dynamic diluter. 100 1:1 7
Oven program 100 °C (4.0 min hold), 10 °C/min to 160 °C
(2.0 min hold)
Experimental Column velocity 54.189 cm/s
Injection Non-heated gas sample valve
Standards and reagents
Transfer line Ambient
The standards and reagents used are listed in Table 1. temperature
Detector TCD
Table 1. Standards and Reagents Detector temp 160 °C
Reference flow 15 mL/min
Standard Reagent
1 HFC-134a, HFC-152a, and CO2 Matheson- Trigas 33% Each
Results
2 Butane, propane, isobutane, Matheson-Trigas 25% Each
Dimethyl ether The HP-PLOT Q column provides baseline resolution for the
seven propellants analyzed. The inlet split ratio was varied to
obtain a calibration curve across six points. See Tables 3 and
Instrument 4 for a correlation of split ratio to percent volume of component
The analysis was performed on an Agilent 7890A gas chro- injected. Linearity was good for all seven components with
matograph equipped with a 6-port gas sample valve, a R2 ranging from 0.9982 to 0.9994. Figures 3 and 4 show the
split/splitless capillary inlet, an HP-PLOT Q capillary column calibration curves for each component by varying the inlet split
and an Agilent thermal conductivity detector. ratio from 1:1 to 47:1.
Figure 1 Shows good resolution and sensitivity between carbon
Sample preparation dioxide, HFC-134a, and HFC-152a at a concentration of 33%
All samples were prepared by loading Tedlar sample bags from volume each on a TCD using the method parameters for
a bulk supply standard. All standard concentrations are stated screening.
in percent volume. Calibration samples were prepared from the Figure 2 shows good resolution and sensitivity between
stock gas cylinders provided by Matheson-Trigas. Stock stan- propane, dimethyl ether, isobutane, and n-butane at a concen-
dard solutions used in calibrations are described as Standard 1: tration of 25% volume each on a TCD using the method
HFC-134a (33%), HFC-152a (33%), and carbon parameters for screen screening.

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Table 3. Table of TCD Response Table 5. Linear Regression Analysis

Amount
Split ratio
Carbon
HFC-134a HFC-152a
Compound R2
(% vol) dioxide
Carbon dioxide 0.9984
1.65 47.114:1 1087.4 1660 1381.2
3.30 22.843:1 2051.7 3077.5 2772.1 HFC-134a 0.9994

6.60 10.707:1 4135.1 6472.5 5750.1 HFC-152a 0.9991

16.50 3.425:1 10162.3 16429.2 14298.9 Propane 0.9989

24.75 1.8:1 14832.8 24254.5 20917.5 Dimethyl ether 0.9986

33.00 1:1 19122.8 31600.1 27201.5 Isobutane 0.9991
n-Butane 0.9982
Table 4. Table of TCD Response

Amount Dimethyl
(% Vol) Split ratio Propane ether Isobutane n-Butane
1.25 47.114 : 1 1334.7 1231 1561.5 1619

2.50 22.843 : 1 2960.3 2660.6 3513.8 3628

5.00 10.707 : 1 6113.8 5533.3 7280.5 7549

12.50 3.425 : 1 14875.5 13527.8 17859.6 18629.3

18.75 1.8 : 1 21761.5 19797.5 26245.2 26724.3

25.00 1:1 28315.7 25563.2 34117.2 34734.5

Figure 1. Chromagram of CO2, HFC-134a, and HFC-152a.

3
Figure 2. Chromagram of propane, dimethyl ether, isobutane, n-butane.

4
Figure 3. Six point calibration curve from 1.65% to 33% for Carbon Dioxide, HFC-134a, and HFC-152a. Split ratio range from 1:1 to 47:1.

Figure 4. Six point calibration curve from 1.25% to 25% for propane, dimethyl ether, iso-butane, n-butane. Split ratio range from 1:1 to 47:1.

5
Conclusion References
Analysis of consumer propellants can be achieved using a 1. Aerosol Propellants, The Alliance for Responsible
basic Agilent GC configured with a gas sample valve, split inlet, Atmospheric Policy, April 12, 2011,
HP-PLOT Q column, and a TCD detector. The split inlet can be http://www.arap.org/docs/aerosol.html
used to dynamically dilute samples. This is useful when a mul-
2. California Environmental Protection Agency Air Resource
tipoint calibration is needed across a fairly narrow range of
Board, Special Analysis Section Northern Laboratory
analysis. It was observed that split ratios up to 600:1 could
Branch Monitoring and Laboratory Division, October 17,
produce very linear results.
2003, Standard Operating Procedure for the
Determination of Exempt Compounds in Aerosol
Consumer Product Propellant by Gas Chromatography,
Revision 2.1

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