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
• 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:
