HEADSPACE

TECHNIQUES
A Modern Sampling Preparation for
volatile analytes
 Topics
General Introduction
Strengths and Weaknesses
Basic Operation (Short Video Presentation)
Application
 General Introduction
Volatile compounds vaporize partially into gas phase
and back again into the sample. After some time it
reaches equilibrium.

By taking the aliquot of the gas phase, we can analyze

volatile compounds without interference by the non
volatile compound.
 General Introduction
Let us consider analysis of perfume. It contains
water, alcohol, essential oils, etc.
 General Introduction
If we put this sample in a sealed vial, heat it at 60
degrees celsius for a certain period of time what
happens to the molecules of perfume inside the vial?

More volatile compounds go to the headspace. More

volatile more concentrated goes to the headspace.
Crude separation has been achieved
 General Introduction
Chromatography will be much cleaner, easier and
faster.
 Important Notes
The following concepts should be reviewed if you
are going to develop a method using headspace
gas chromatography:

o Partition coefficient = ; CS= conc of compound in sample phase, CG=

conc of compound in headspace phase
Migration of compounds into the headspace phase does not just
depend on their volatility but more on their affinity for the original
sample phase.
o Phase Ratio
o Vapor Pressures and Daltons Law
o Raoults Law
o Activity Coefficients
o Henrys Law
 Important Notes
The following parameters are very important in the
HS- GS analysis
o Sample Volume
o Temperature
o Pressure
o Modifying Sample Matrix
o Equilibration time
 Types of headspace
techniques
Static Headspace-only the volatiles in a set volume
of the headspace obtained

Dynamic Headspace-the volatiles are

concentrated on a trap
Strengths and Weaknesses
Strengths
o Can analyze a variety of matrices
(liquids, soil, polymer, fabrics, gels, emulsions, etc)
Very useful in prescreening analysis of unknown and contaminated
samples
o Analysis at low concentration
o Analysis without interference of the non- volatile matrix
Extends column life
o Minimal sample preparation time

Weakness
o Only up to mid-ppb levels
o Evaluation of polar compounds is difficult at low- levels
Basic Operation
Application
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