Lehrstuhl für Siedlungswasserwirtschaft

Ingenieurfakultät Bau Geo Umwelt

Technische Universität München

Supercritical Fluid Chromatography

PD Dr. J. Graßmann; PD Dr. T. Letzel

Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Supercritical Fluid Chromatography

• SFC was originally called Supercritical Fluid Chromatography, but in the
way this technique is used nowadays, this name is misleading and
confusing.
• SFC was first reported in 1962 by Ernst Klesper, but it took many years,
until the potential of this technique was recognized.
• SFC is now a re-emerging technique, but information about basic
mechanisms is often scarce.
• Many compounds were and can be used as mobile phase. Finally carbon
dioxide prevailed, because of its moderate supercritical point and its green
character.
• SFC is nowadays explained as chromatography with carbon dioxide.

PD Dr. J. Graßmann; PD Dr. T. Letzel

Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Supercritical Fluid Chromatography

1962: Introduction of SFC by Klesper et. al 1

• ‚High pressure gas chromatography

above critical temperatures‘
• Capillary SFC
• System optimization

1990er: packed column SFC

• Further developments
• More stable systems

2010/2012: Introduction of the

new SFC generation (1) Klesper, E.; Corwin, A. H.; Turner, D. A. High Pressure Gas Chromatography
above Critical Temperatures. J. Org. Chem. 1962, 27, 700–701.

PD Dr. J. Graßmann; PD Dr. T. Letzel

Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Supercritical Fluid Chromatography

What means “supercritical”?

• Supercritical is a thermodynamical
state, which lies above the
supercritical point.

• At critical pressure and critical

temperature a state between liquid
and gaseous is reached.

• The viscosity of a supercritical fluid

is comparable to a gas and the
density is liquid-like.

PD Dr. J. Graßmann; PD Dr. T. Letzel

Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Supercritical Fluid Chromatography

Why CO2 as mobile phase?

• Moderate supercritical conditions

• Not corrosive above the critical

point

• Environmentally neutral:
• CO2 is a waste product of
industrial processes

• Avoids the generation of CO2

for production or disposal of
other organic solvents
• Less energy required to
GREEN
evaporate mobile phase after
SEPARATIONS
separations

PD Dr. J. Graßmann; PD Dr. T. Letzel

Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Supercritical Fluid Chromatography

SFC bridges the gap between
gas chromatography (GC) and liquid chromatography (LC)

• Gaseous mobile • Supercritical mobile • Liquid mobile phase

GC

SFC

LC
phase phase
• Separation by solvent
• Separation by • Separation by solvent gradient
temperature gradient and density gradient

• Limited variety of • Huge variety of • Huge variety of

stationary phases stationary phases stationary phases

• No limitation in • Modifiers and • Limitation by in

stationary phase additional factors to column pressure
length modifiy selectivity drop

PD Dr. J. Graßmann; PD Dr. T. Letzel

Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Supercritical Fluid Chromatography

GC LC

SFC

Efficiency Efficiency

Selectivity Selectivity

Efficiency

PD Dr. J. Graßmann; PD Dr. T. Letzel Selectivity

Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Supercritical Fluid Chromatography

Instrumentation:

• Comparable setup to LC systems

• To ensure a constant mobile phase condition in the whole system, pressure

and temperature must be controlled carefully

• Back pressure regulator (BPR) helps to prevent changes in solvent

conditions by in-column pressure drop

• Modifiers and additives are used to modify elution strength of the mobile
phase.
• Modifiers: methanol, ethanol or isopropanol, etc.
• Additives: Salts, acids or water, etc.

• Various systems commercially available since 2010/2012

PD Dr. J. Graßmann; PD Dr. T. Letzel

Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Supercritical Fluid Chromatography

Instrumental setup:

CO2 Modifier

Binary pump

Back
Autosampler
Pressure
Regulator

Advanced
Column BPR detectors like
oven mass
spectrometry
UV-Vis detector

PD Dr. J. Graßmann; PD Dr. T. Letzel

Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Supercritical Fluid Chromatography

For which kind of separations is SFC ideal?

• Chiral:

• Normal phase: Separations of polar molecules. SFC requires less organic

solvent compared normal phase LC

• Structural isomers:

PD Dr. J. Graßmann; PD Dr. T. Letzel

Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Supercritical Fluid Chromatography

Supercritical conditions are often not necessary for successful separations:

Supercritical conditions: Conditions below critical point:

PD Dr. J. Graßmann; PD Dr. T. Letzel

Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Supercritical Fluid Chromatography

Summary:

• SFC is a new, old separation technique, which utilizes carbon dioxide as

mobile phase

• It provides benefits of both, GC and LC and offers a different selectivity

• The elution strength of the mobile phase can be altered by using modifiers
and additives

• The instrumental setup is comparable to LC, but more factors than in LC

(temperature and pressure) influence the retention of compounds

PD Dr. J. Graßmann; PD Dr. T. Letzel