Headspace

Rüder Schill
Objectives
• Get an overview of Headspace Sampling Technique
• Obtain an understanding of the Agilent product offering

Understand differences between our Headspace Samplers

• Get an understanding of available sales tools/ literature

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After this presentation, you should be
able to…
• Understand Headspace Sampling Technique
• Quote a Headspace Sampler
• Find available literature on our Headspace Sampler
• Be familiar with key applications for Headspace Sampling

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Headspace Sampling Technique

 Very clean vapor above the

sample is removed and analyzed

 A wide range of sample matrices

can be handled

 Sample preparation is minimal

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Headspace Sampling for Volatiles

 Place the sample in the vial and

crimp the cap/septum in place

 Thermostat (incubate) for a fixed

time

 Deliver a reproducible volume of

the headspace gas to the GC

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Headspace Vapor Phase Concentrations

V
G
After equilibration CG
Equilibration
K = C / CG
L
(distribution coefficient) V
C CL L
0

From mass balance :

C 0 x V L = C G x V G + C L x VL

Rearranging :

Cg = C0 / (K + Vg / VL)

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Headspace Vapor Phase Concentration

C G V G
Matrix effects
CG = C / (K + V / V )
0 G L
K = C L / CG (distribution coefficient) C L VL

K depends on both the analyte and the matrix

Analyte Solvent K (25 C)
Toluene decane ~ 3000
Toluene water ~ 4 *
Ethanol decane ~ 60 *
Ethanol water ~ 5000
Ethanol water satd with Na 2SO4 ~ 300 *

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Headspace Sampling Method

Standby He
Loop

Vent

Pressurization He
Loop

Vent

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Headspace Sampling Method

Venting He
Loop

Vent

Injection He
Loop

Vent

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Headspace Can Be Very Sensitive !

1-3 uL 1-3 mL

If Cgas = Cliquid
Headspace sampling will be
about 500x more sensitive
than liquid sampling !

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Head Space Applications
• Residual solvents in pharmaceuticals
• Blood alcohol and toxicology screening
• Residual solvents, additives, or monomers in
polymer or plastic products (food packaging)
• Food and Flavor products including beverages
• Water analysis
• LUST, soil, sludge, chem spills, fertilizers, plants
• Fermentation products or processes (inc. BioChem)
• Transformer Oil Gas analysis
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HSS-GC Application: USP <467>
• Evaluating Organic Volatile Impurities (OVI) in Pharmaceutical Formulations
and excipients
• Acceptable Method: SL-GC; HSS-GC and P&T-GC
• Solvent of interest:

Methylene Chloride 100 ppm

Benzene 100 ppm

Trichlorethylene 100 ppm

1,4 - Dioxane 100 ppm

Chloroform 50 ppm
• Evaluation by Gudat and Sievert concluded the HSS - GC was preferred in
three methods due to the high sensitivity for CHCl3
• Reference: Headspace Analysis of Organic Volatile Impurities by USP <467>
Using the HP-624 and the HP-Fast GC Residual Solvent Column (P/N: 5968-
4586E, 1999)

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HSS-GC Application: USP 467

1 Methylene Chloride (25 ppm)

2 Chloroform (12 ppm)
3 Benzene (25 ppm)
3 4 Trichloroethylene (25 ppm)
5 1, 4-Dioxane (25 ppm)

4 5
2

2 4 6 8 10

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HSS-GC Application: Common Solvent
1. Methanol 12. Ethylacetate
2. Ethanol 13. Tetrahydrofuran
3. Ether 14. S-Butanol
4. Acetone 15. Chloroform
5. i-Propanol 16. Cyclohexane
3 6. Acetonitrile 17. Benzene
7. Methylene chloride 18. Heptane
8. t-butanol 19. Trichloroethylene
9. Hexane 20. 1,4-Dioxane
4 13,14 10. Propanol 21. Pyridine
17 11. Methylethylketone 22. Toluene

5 8 11
9 12 16
10 22
18
2 6 19
20 21
1 17
15

0 2 4 6 8 10 12 14 min

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HSS-GC Application: Blood-Alcohol
Analysis
• Blood-Alcohol Analysis Background:

Public demand to restrict drunk drivers

Demand for reliable blood-alcohol analyzers - police departments

Require high precision, accuracy, and speed.

Results could be challenged in court

Agilent’s HSS-GC systems have been used in almost every state
police department in USA and in many other countries.
• Reference: Blood Alcohol Analysis Using the HP-Blood Alcohol
Column - Paper presented by Dennis Gere - Pittcon 2000

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HSS-GC Application: Blood-Alcohol
Analysis

Chromatogram of 0.1 g/ 100mL

Standard
pA Acetaldehyde

50

45
n-propanol 2.2 min
40 Acetone
35

30

25
Ethanol
20 Methanol i-propanol n-butanol
15

10
0.5 1 1.5 2 2.5 min

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7694 Headspace Sampler

Nothing or flow/
pressure control

44 vials
Robotic arm

Serial I/O for PC

Heated air oven with

intelligent vial delivery
Full feature set

G1290B = Manual flow control

G1289B = Uses EPC from GC

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7694E Economy Headspace (G1883A)

Just enough features

at the right price
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Headspace Sampler Products Family
Product Feature set Benefit

Design
Flow and pressure controllers are built-in.
Carousel holds 12-vials (10 or 20mL).
Automated sequence (4-method chaining).
Nickel transfer line to the GC.
Sends remote start/stop to GC/Integrator.
Easy to modify for EPC control.
- Provides control for HS & GC gases, and
simplifies moving unit from GC to GC.
- Twelve vials are analyzed automatically.
- More inert than stainless steel.
- Controls the run (HP "GC READY" sensed).
- Adaptable to manual or EPC systems.

Headspace analysis procedure

Constant vial heating time.
Time or temperature setpoint incrementing.
Vial temperature range to 200C.
Ambient vial shaking.
G1883A Economy Headspace
- Eliminates variability of manual methods.
- Automates method development process.
- Homogenizes the sample.

Design (as above, but;)

Autosampler tray holds 44-vials (carousel: 6). - Automation/productivity for high volume lab
Optional sample flowpath of Silcosteel. - Ultimate inertness for sensitive chemicals.
Serial communications RS-232C I/O port; with
- System control localized, from the PC or
optional external PC/SW or Integrator control.
the Integrator keyboard.
Headspace analysis procedure (as above but;)
Heated vial shaking. - May shorten the sample equilibration time.
Multiple headspace extraction capability - Useful for volatiles in an insoluble matrix.
G1290B Standard Headspace
Design (see G1290A, but;)
Flow and pressure control provided by EPC-GC. - Unique reproducibility & programability.
G1289B System Headspace
Headspace analysis procedure (see G1290A)

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Headspace: Supporting Literature
HP 7694 Brochure 5965-3424E
HP 7694 Ordering and Specifications guide 5968-1913E
HP 7674E Brochure 5965-4767E/G
Retention Time Locking Using USP 467 Standard Sample and Automated Headspace 5968-3760E
Headspace Analysis of Organic Volatile Impurities by USP <467> Using the HP-624 and
the HP-Fast GC residual Solvent Column 5968-4586E
Headspace Analysis of Residual Ethylene Oxide in Sterilized Medical Devices 5966-4034E
Improving Environmental Lab Efficiency by Screening VOC’s 5965-1436E
Multiple Headspace Extraction - Capillary Gas Chromatography for the Quantitative
Determination of Volatiles in Solid Matrices Application Note 228-356 5965-0978E
Analysis of Sulfur Compounds in Commercial Beers 5963-6636E
The Use of Static and Dynamic Headspace Sampling for the Trace Analysis of Volatile
Organic Pollutants in Environmental Samples 5962-8584E
Multiple Headspace Extraction-Capillary Gas Chromatography for the Quantitative
Determination of Fragrances in Shampoo 5962-7216E
Analysis of Organic Impurities in a Recycled Paper Product 5091-9585E
Analysis of Volatile hydrocarbons and ketones in blood 5091-8946E

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Key Points to Remember
• Headspace technique gets the cleanest sample into the GC
• Useful technique for a wide range of matrices including solids
• Headspace technique can be very sensitive
• Agilent offers family of Headspace Samplers - three models
• For sensitive or reactive compounds recommend SilcoSteel
pathway (Option 100 or Accessory G1286A)

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