Supelco Ionic Liquid GC Columns Introduction to the Technology Updated: -Jan-203 Agenda Overview GC Column Polarity Scale Temperature Effects on Selectivity Column Selectivity: QC Test Mix (0.2 mm I.D. Columns) Rapeseed Oil FAMEs (0.2 mm I.D. Columns) QC Test Mix (0.0 mm I.D. Columns) Column Specifications and Phase Structures Summary sigma-aldrich.com/analytical
Overview 2
Structures of Non-Ionic Liquid GC Phases Polysiloxane Polymer Phases (92) Polyethylene Glycol Phases (~96) Active hydroxyl (-OH) groups at the polymer termini allow a back-biting reaction Resulting in phase degradation Contributing to column bleed Chemistry modifications are limited to pendent group changes Active hydroxyl (-OH) groups at the polymer termini allow a back-biting reaction Resulting in phase degradation Contributing to column bleed Very limited chemistry modifications possible Limited to 280 ºC maximum temperature R = methyl, phenyl, fluoropropyl, and/or cyanopropyl (listed from least polar to most polar). x,y = percentage in the overall polymer composition. n = number of monomer repetitions to make the overall polymer. 3
Structure of an Ionic Liquid GC Phase Phase used to make the SLB-IL00,9-Di(3-vinylimidazolium)nonane bis(trifluoromethylsulfonyl)imide Much smaller No active hydroxyl groups Many modifications possible Dicationic or polycationic Numerous cation, linkage, and anion choices Pendant groups can be added J.L. Anderson, R. Ding, A. Ellern, and D.W. Armstrong, Structure and Properties of High Stability Geminal Dicationic Ionic Liquids J. Am. Chem. Soc. 27 (200) p. 93. 4
GC Column Polarity Scale
Description of Our Procedure Each column is characterized with a series of five probes plus several n-alkane markers to determine the retention index for each probe Benzene Butanol 2-Pentanone Nitropropane Pyridine McReynolds Constants are then calculated using the retention index data of the column relative to the retention index data for the same five probes on squalane, the most nonpolar GC stationary phase The five McReynolds Constants are summed to obtain Polarity (P) values, which are then normalized to SLB-IL00 (set at P=00) to obtain Polarity Number (P.N.) values Our procedure was proposed by Prof. Luigi Mondello (University of Messina, Italy). 6
Visual Representation 7
Experimentally Determined Polarity Numbers P (Polarity) = sum of the first McReynolds Constants. P.N. (Polarity Number) = Polarity (P) normalized to SLB-IL00 (set at P=00). 8
Temperature Effects on Selectivity 9
Temperature Effects on Selectivity An Example 80 ºC isothermal.8 2.0 2.2 2.4 00 ºC isothermal,.8 2.0 2.2 2.4 0 ºC isothermal 2 3 4 2 3 4.8 2.0 2.2 2.4 2 Peak IDs (in boiling point order). Toluene 2. Ethylbenzene 3. p-xylene 4. Isopropylbenzene. n-tridecane (C3) 3 4 Higher oven temperature: Decreased retention; expected, a higher temperature will weaken all interactions Selectivity changes n-tridecane (peak ) is primarily retained by dispersive interactions The aromatics are retained by dipole and induced dipole interactions in addition to dispersive interactions column: SLB-IL00, 30 m x 0.2 mm I.D., 0.20 µm (28884-U) inj.: 20 ºC det.: FID, 20 ºC carrier gas: helium, 30 cm/sec injection:.0 µl, 00: split liner: 4 mm I.D., split, cup design sample: each analyte at various concentrations in isooctane 0
Temperature Effects on Selectivity Manipulate Oven Temperature to Optimize Separations This is exhibited by all columns (ionic liquid and non-ionic liquid) The greater the polarity of the column, the more pronounced the effect Highly polar and extremely polar columns fully demonstrate this effect Intermediate polar and polar columns show this effect to a much lesser degree Non-polar columns rarely demonstrate this effect Oven temperature and/or ramp rate can both be adjusted Want to optimize a separation? Try slight oven temperature changes (0 ºC up or down), or slight ramp rate changes ( ºC /min faster or slower) Need to duplicate a published chromatogram? Use the identical oven temperatures and ramp rates
Column Selectivity QC Test Mix (30 m x 0.2 mm I.D., 0.20 µm Dimensions) 2
30 m x 0.2 mm I.D., 0 ºC Isothermal 3 4 6 SLB-IL9 2 8 7 2.0 3.0 4.0.0 3 4 6 SLB-IL60 2 8 7 2.0 3.0 4.0.0 3 4 6 SLB-IL6 2 8 7 2.0 3.0 4.0.0 3
30 m x 0.2 mm I.D., 0 ºC Isothermal 3 4 6 2,8 7 SLB-IL76 2.0 3.0 4.0.0 3 4 6 SLB-IL82 8 2 7 2.0 3.0 4.0.0 3 4 6 SLB-IL00 8 2 7 2.0 3.0 4.0.0 3,4 6 SLB-IL 8 2 4 7 2.0 3.0 4.0.0
QC Test Mix Peak IDs & Conditions Peak IDs (listed in boiling point order). Toluene 2. Ethylbenzene 3. p-xylene 4. Isopropylbenzene (Cumene). Cyclohexanone 6.,2,4-Trimethylbenzene 7.,2,4,-Tetramethylbenzene 8. n-tridecane (C3) Conditions columns: 30 m x 0.2 mm I.D., 0.20 µm oven: 0 ºC inj.: 20 ºC det.: FID, 20 ºC carrier gas: helium, 26 cm/sec injection:.0 µl, 00: split sample: each analyte at various concentrations in isooctane
Column Selectivity Rapeseed Oil FAMEs (30 m x 0.2 mm I.D., 0.20 µm Dimensions) 6
30 m x 0.2 mm I.D., 0 ºC Isothermal SLB-IL9 2 4 3 6 7 Peaks 9-8 0 0 20 SLB-IL60 2 4 3 6 7 Peaks 9-8 0 0 20 SLB-IL6 2 4 3 6 7 Peaks 9-8 0 0 20 7
SLB-IL76 30 m x 0.2 mm I.D., 0 ºC Isothermal 2 4 3 6 7 8 9 0 0 0 20 SLB-IL82 2 4 3 7 6 9 0 8 0 0 20 SLB-IL00 2 4 3 7 8 6 9 0 0 0 20 SLB-IL 2 4 3 7 6,9 0 8 0 0 20 8
Rapeseed Oil FAMEs Peak IDs & Conditions Peak IDs. Myristic (C4:0) @.0 % 2. Palmitic (C6:0) @ 4.0 % 3. Stearic (C8:0) @ 3.0 % 4. Oleic (C8:n9c) @ 60.0 %. Linoleic (C8:2) @ 2.0 % 6. Linolenic (C8:3) @.0 % 7. Arachidic (C20:0) @ 3.0 % 8. cis--eicosenoic (C20:) @.0 % 9. Behenic (C22:0) @ 3.0 % 0. Erucic (C22:) @.0 %. Lignoceric (C24:0) @ 3.0 % Conditions columns: 30 m x 0.2 mm I.D., 0.20 µm oven: 80 ºC isothermal inj.: 20 ºC det.: FID, 20 ºC carrier gas: helium, 2 cm/sec constant injection:.0 µl, split 00: liner: 4 mm I.D., split type, cup design 9 sample: Rapeseed oil FAME mix (O776-AMP) diluted to 0 mg/ml in methylene chloride
FAME Equivalent Chain Length (ECL) Values 30 m x 0.2 mm I.D., 80 ºC Isothermal 20
Column Selectivity QC Test Mix ( m x 0.0 mm I.D., 0.08 µm Dimensions) 2
m x 0.0 mm I.D., 90 ºC Isothermal 3 4 SLB-IL9 2 6 8 7.0 2.0 SLB-IL60 chromatogram coming soon 3 SLB-IL6 4 6 2 8 7.0 2.0 22
m x 0.0 mm I.D., 90 ºC Isothermal 3 4 6 2 8 7 SLB-IL76.0 2.0 8 3 4 SLB-IL82 2 6 7.0 2.0 3 4 6 SLB-IL00 2 8 7 3,4.0 2.0 SLB-IL 8 2 6 7.0 2.0 23
QC Test Mix Peak IDs & Conditions Peak IDs (listed in boiling point order). Toluene 2. Ethylbenzene 3. p-xylene 4. Isopropylbenzene (Cumene). Cyclohexanone 6.,2,4-Trimethylbenzene 7.,2,4,-Tetramethylbenzene 8. n-tridecane (C3) Conditions columns: m x 0.0 mm I.D., 0.08 µm oven: 90 ºC inj.: 20 ºC det.: FID, 20 ºC carrier gas: hydrogen, 0 cm/sec injection: 0. µl, 300: split sample: each analyte at various concentrations in isooctane 24
Column Specifications and Phase Structures In Order of Increasing Polarity Number (P.N.) 2
SLB-IL9 Column Specifications Application: This polar ionic liquid column has a polarity/selectivity similar to that of polyethylene glycol (PEG) columns (usually have wax in the product name), but with a higher maximum temperature (300 ºC compared to 270-280 ºC). This increased temperature allows faster analyses to be achieved and/or additional analytes with higher boiling points to be analyzed. This combination of a high thermal limit and an orthogonal selectivity to non-polar columns also makes it a good GCxGC column choice. Launched in 2009. USP Code: None Phase: Non-bonded;,2-Di(tripropylphosphonium)dodecane bis(trifluoromethylsulfonyl)imide Temp. Limits: Subambient to 300 ºC (isothermal or programmed) Catalog Numbers 28880-U, m x 0.0 mm I.D., 0.08 µm 2889-U, 30 m x 0.2 mm I.D., 0.20 µm 26
SLB-IL9 Phase Structure,2-Di(tripropylphosphonium)dodecane bis(trifluoromethylsulfonyl)imide 27
SLB-IL60 Column Specifications Application: The SLB-IL60 polar ionic liquid column has a polarity/selectivity similar to that of polyethylene glycol (PEG) columns (usually have wax in the product name), but different enough to provide a unique elution pattern. It also has a higher maximum temperature of 300 ºC, compared to 20-280 ºC for most PEG columns. These features make it an excellent alternative to existing wax columns. The combination of a high thermal limit and an orthogonal selectivity to non-polar columns also makes it a good GCxGC column choice. Launched in 202. USP Code: None Phase: Non-bonded;,2-Di(tripropylphosphonium)dodecane bis(trifluoromethylsulfonyl)imide Temp. Limits: 3 ºC to 300 ºC (isothermal or programmed) Catalog Numbers 290-U, 30 m x 0.2 mm I.D., 0.20 µm 28
SLB-IL60 Phase Structure,2-Di(tripropylphosphonium)dodecane bis(trifluoromethylsulfonyl)imide 29
SLB-IL6 Column Specifications Application: This polar column, the first of our third generation ionic liquid columns, has a polarity/selectivity close to that of the SLB-IL9 due to structural similarities. This column has a polarity/selectivity similar to that of polyethylene glycol (PEG) columns (usually have wax in the product name), but with a higher maximum temperature (290 ºC compared to 270-280 ºC). Launched in 200. USP Code: None Phase: Non-bonded;,2-Di(tripropylphosphonium)dodecane bis(trifluoromethylsulfonyl)imide trifluoromethylsulfonate Temp. Limits: 40 ºC to 290 ºC (isothermal or programmed) Catalog Numbers 29484-U, m x 0.0 mm I.D., 0.08 µm 29486-U, 30 m x 0.2 mm I.D., 0.20 µm 30
SLB-IL6 Phase Structure,2-Di(tripropylphosphonium)dodecane bis(trifluoromethylsulfonyl)imide trifluoromethylsulfonate 3
SLB-IL76 Column Specifications Application: This highly polar column was the first of our second generation ionic liquid columns. It is engineered with a phase structure that allows numerous analyte solvation interactions that are not possible with other columns (non-ionic liquid columns as well as ionic liquid columns), resulting in selectivity differences even when compared to columns with similar GC column polarity scale values. Launched in 2009. USP Code: None Phase: Non-bonded; Tri(tripropylphosphoniumhexanamido)triethylamine bis(trifluoromethylsulfonyl)imide Temp. Limits: Subambient to 270 ºC (isothermal or programmed) Catalog Numbers 28909-U, m x 0.0 mm I.D., 0.08 µm 2893-U, 30 m x 0.2 mm I.D., 0.20 µm 32
SLB-IL76 Phase Structure Tri(tripropylphosphoniumhexanamido)triethylamine bis(trifluoromethylsulfonyl)imide 33
SLB-IL82 Column Specifications Application: This highly polar ionic liquid column is most similar in polarity to non-ionic liquid columns that contain a polysiloxane phase with a high percentage of cyanopropyl pendent groups. It provides an alternate selectivity to these cyanopropyl siloxane columns, and is less susceptible to damage from oxygen/moisture. Launched in 200. USP Code: None Phase: Non-bonded;,2-Di(2,3-dimethylimidazolium)dodecane bis(trifluoromethylsulfonyl)imide Temp. Limits: 0 ºC to 270 ºC (isothermal or programmed) Catalog Numbers 29477-U, m x 0.0 mm I.D., 0.08 µm 29479-U, 30 m x 0.2 mm I.D., 0.20 µm 34
SLB-IL82 Phase Structure,2-Di(2,3-dimethylimidazolium)dodecane bis(trifluoromethylsulfonyl)imide 3
SLB-IL00 Column Specifications Application: This highly polar column was the world s first commercially available ionic liquid GC column. It serves as the benchmark of 00 on our GC column polarity scale. Compared to a TCEP column (almost identical polarity/selectivity), the SLB-IL00 is more thermally stable, plus more resistant to damage from moisture/oxygen. Launched in 2008. USP Code: None Phase: Non-bonded;,9-Di(3-vinylimidazolium)nonane bis(trifluoromethylsulfonyl)imide Temp. Limits: Subambient to 230 ºC (isothermal or programmed) Catalog Numbers 28882-U, m x 0.0 mm I.D., 0.08 µm 28883-U, 20 m x 0.8 mm I.D., 0.4 µm 28884-U, 30 m x 0.2 mm I.D., 0.20 µm 28886-U, 60 m x 0.2 mm I.D., 0.20 µm 28887-U, 30 m x 0.32 mm I.D., 0.26 µm 28888-U, 60 m x 0.32 mm I.D., 0.26 µm 36
SLB-IL00 Phase Structure,9-Di(3-vinylimidazolium)nonane bis(trifluoromethylsulfonyl)imide 37
SLB-IL Column Specifications Application: This extremely polar ionic liquid column was the world s first commercial column to rate over 00 on our GC column polarity scale. It has very orthogonal selectivity compared to commonly used non-polar and intermediate polar columns, providing increased selectivity for polar and polarizable analytes. Its temperature limit of 270 ºC is very impressive for such an extremely polar column. The 60 m version is excellent at resolving benzene and other aromatics in gasoline. The 00 m version is suitable for detailed cis/trans FAME isomer analysis, and is a great complementary column to the SP-260. Launched in 200. USP Code: None Phase: Non-bonded;,-Di(2,3-dimethylimidazolium)pentane bis(trifluoromethylsulfonyl)imide Temp. Limits: 0 ºC to 270 ºC (isothermal or programmed) Catalog Numbers 2892-U, m x 0.0 mm I.D., 0.08 µm 28927-U, 30 m x 0.2 mm I.D., 0.20 µm 28928-U, 60 m x 0.2 mm I.D., 0.20 µm 29647-U, 00 m x 0.2 mm I.D., 0.20 µm 38
SLB-IL Phase Structure,-Di(2,3-dimethylimidazolium)pentane bis(trifluoromethylsulfonyl)imide 39
Summary 40
Outlook for the Future Ionic liquids have the opportunity to impact current GC and GC-MS practices along several paths Columns can be engineered with identical selectivity to non-ionic liquid columns but with higher operating temperatures and less susceptibility to damage from moisture and/or oxygen. Columns can be engineered with completely unique selectivity to non-ionic liquid columns producing good peak shape and resolution for compounds of varying functionality. Columns can be used in multidimensional separations due to their engineered orthogonality and high thermal stability. 4
To Learn More Visit our ionic liquid GC column landing page (www.) Product information Technical literature Application notes Bibliography 42