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Static Headspace

Definition

A sample preparation technique in which a sealed vial is heated until volatile analytes reach thermodynamic equilibrium between the liquid matrix and the gas above it; the gas phase (headspace) is injected into the GC column.

Sample state
Sealed, heated vial at equilibrium
Injected phase
Gas above the liquid matrix
Principle
Thermodynamic equilibrium between liquid and gas phases
Common use
Ethanol analysis by GC-headspace

Common questions

Why is static headspace preferred over direct injection for blood alcohol analysis?+

Injecting whole blood directly would contaminate and damage the GC column over repeated runs. Sampling only the equilibrated vapour above the sample keeps volatile ethanol quantifiable while leaving non-volatile blood components out of the instrument.

What can go wrong if the headspace vial has not reached full equilibrium before sampling?+

An incomplete equilibrium underrepresents the true vapour concentration of ethanol relative to the liquid, producing a falsely low reading, which is why fixed incubation time and temperature are tightly controlled in the method.

Related terms

2100:1 Partition Ratio
The conventional blood/breath partition assumption used by breath alcohol analysers worldwide: 2100 mL of venous blood contains the same mass of ethanol...
Beta Elimination Rate (Beta)
The rate at which BAC falls during the post-absorptive phase of alcohol metabolism, expressed as mg/100 mL/hour. Population mean approximately 15 mg/100...
Blood Alcohol Concentration (BAC)
Mass of ethanol per unit volume of whole blood, expressed as mg per 100 mL (equivalent to mg/dL or mg%), or as...
DB-ALC1 / DB-ALC2
A matched pair of Agilent fused-silica GC columns used for dual-column orthogonal confirmation of blood ethanol. DB-ALC1 uses a polyethylene glycol stationary...
Internal Standard (IS)
A compound chemically near-identical to the analyte, often a deuterated isotopologue (d3-morphine, d5-EDDP, d5-alprazolam, pyrene-d10), spiked into every sample at a known...
NIST SRM 1828
A series of NIST-certified reference material aqueous ethanol standards (0.02 to 0.40 per cent w/v) used to calibrate forensic blood ethanol analytical...
Partition Coefficient (K)
The ratio of analyte concentration in the liquid phase to concentration in the gas phase at equilibrium. For ethanol in blood at...
Sodium Fluoride / Potassium Oxalate (Grey-Top Tube)
The standard blood collection tube for forensic ethanol analysis. Sodium fluoride inhibits microbial fermentation (which would produce artefactual ethanol post-collection); potassium oxalate...
Widmark Factor (Rho / R)
A dimensionless pharmacokinetic constant that represents the distribution of ethanol across body water. Averages approximately 0.68 for adult males and 0.55 for...

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