Allen K. Vickers Applications Engineer Manager December 6, 2000 PLOT Column Selection (or How to Retain Your Gases) Telephone Number: 816-650-0621 Chair Person: Lisa Lloyd WCOT vs. PLOT Stationary Chromatographic Stationary Type Phase Process Phases WCOT Liquid or Gas / Liquid Polysiloxanes gum partition PEG PLOT Solid Gas solid Porous Polymers, adsorption Al2O3, Zeolites, etc. Dial 1-816-650-0621 for e-Seminar Audio Why Use PLOT Columns? • Enhanced retention • Enhanced selectivity • Permit higher initial oven temperatures than WCOT Dial 1-816-650-0621 for e-Seminar Audio PLOT Columns "Solid" Porous Layer Fused Silica Tubing Ideal for the analysis of gases due to their increased retention (k) and unique selectivity (α) compared to WCOT Dial 1-816-650-0621 for e-Seminar Audio WCOT Ethylene Analysis Dial 1-816-650-0621 for e-Seminar Audio PLOT Ethylene Analysis Dial 1-816-650-0621 for e-Seminar Audio Selectivity Interactions in PLOT Phases Shape / Size Surface Zeolites Al2O3 Porous Polymers Bonded Carbon Bonded Silica Molecular Sieves Dial 1-816-650-0621 for e-Seminar Audio J&W / Agilent PLOT Columns • GS-Alumina • HP-PLOT Al2O3 “M” • HP-PLOT Al2O3 “S” • HP-PLOT Al2O3 “KCl” • HP-PLOT MoleSieve • GS-CarbonPLOT • HP-PLOT Q • HP-PLOT U • GS-GasPro Dial 1-816-650-0621 for e-Seminar Audio Al2O3 PLOT Columns •GS-Alumina • HP-PLOT Al2O3 “M” • HP-PLOT Al2O3 “S” • HP-PLOT Al2O3 “KCl” •Different "polarities" due to different salt deactivation treatments Dial 1-816-650-0621 for e-Seminar Audio Surface Interactions in PLOT Columns + + + + + + + + + + + + + neutral δ- δ+ Gas Flow δ- δ+ + + + + + + + + + + + + + • Vapor pressure always plays a leading role in solute interactions Dial 1-816-650-0621 for e-Seminar Audio Dial 1-816-650-0621 for e-Seminar Audio Propylene Impurities Dial 1-816-650-0621 for e-Seminar Audio Crude 1,3-Butadiene Dial 1-816-650-0621 for e-Seminar Audio Extended HC Mixture Dial 1-816-650-0621 for e-Seminar Audio Al2O3 PLOT Column Dimensions Available • “M”, “S” and “KCl” • all available in 0.25, 0.32 and 0.53 mm ID • 15, 30 and 50 meter lengths (depending on ID) • GS-Alumina • available in 0.53 mm ID • 15, 30 and 50 meter lengths Dial 1-816-650-0621 for e-Seminar Audio 0.25 mm ID PLOT Al2O3 “S” Dial 1-816-650-0621 for e-Seminar Audio Al2O3 Column Considerations • Will adsorb water and CO2, affecting retention and resolution. • Recondition at 200°C to restore performance. • Not recommended for analysis of “polar” compounds such as alcohols, sulfurs, ketones, etc. • Upper temperature limit of 200ºC Dial 1-816-650-0621 for e-Seminar Audio Break Number 1 For Questions and Answers Press *1 on Your Phone to Ask a Question Dial 1-816-650-0621 for e-Seminar Audio Molecular Sieve PLOT Columns Size Selectivity )ORZ Zeolite "Backbone" *UDSKLFÃRIÃW\SHÃ.),ÃPROHFXODUÃVLHYH REWDLQHGÃIURPÃWKHÃ,QWHUQDWLRQDOÃ=HROLWH $VVRLFDWLRQÃZHEÃVLWHÃ ZZZL]RRQOLQHRUJ Dial 1-816-650-0621 for e-Seminar Audio Molecular Sieve PLOT Columns • 5Å zeolite for the analysis of fixed and permanent gases: H2, O2, N2, CO, CH4 He, Ne, Ar, Kr, Xe SF6 Dial 1-816-650-0621 for e-Seminar Audio Permanent Gases Dial 1-816-650-0621 for e-Seminar Audio Noble Gases Dial 1-816-650-0621 for e-Seminar Audio Sulfur Hexafluoride Dial 1-816-650-0621 for e-Seminar Audio HP-PLOT MoleSieve • 0.32 and 0.53 mm ID • 15 and 30 meter lengths • Both thin and thick films available • Choose thin film for standard permanent gas analysis • Choose thick film for resolution of argon from oxygen at 35ºC • Upper temperature limit of 350ºC Dial 1-816-650-0621 for e-Seminar Audio Molecular Sieve Column Considerations • Very high retention stationary phase • Can be easily fouled by high MW hydrocarbons and polar compounds • Use pre-column or backflush if necessary • Will adsorb water and CO2 • Columns can be reconditioned by holding at elevated temperature (350ºC) for several hours Dial 1-816-650-0621 for e-Seminar Audio GS-CarbonPLOT • Monolithic carbon layer • Unique selectivity • Phase formed in situ • No particle generation • Extended temperature limit of 360ºC • Not affected by water Dial 1-816-650-0621 for e-Seminar Audio GS-CarbonPLOT Applications • Light hydrocarbons (C1-C5) • Synthesis Gas •H2, CO, CO2, CH4, N2/O2, H2O • Trace CO, CO2 and acetylene in ethylene streams (simplification of ASTM D2505) • Great resolution of air, CO, CO2 and C1-C2 hydrocarbon isomers • Light solvents Dial 1-816-650-0621 for e-Seminar Audio C1 to C3 Hydrocarbons GS-CarbonPLOT 1. Methane 30 m x 0.32 mm I.D., 1.5 µm 2. Acetylene 7 Carrier: He @ 30 cm/s 3. Ethylene Oven: 125°C for 2 min 125°C to 225°C at 20°/min 4. Ethane Injector: Split 1:20, 250°C 5. Propyne Detector: MSD, SIM 6. Propylene 7. Propane 2 4 3 5 6 1 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 Dial 1-816-650-0621 for e-Seminar Audio Natural Gas Mixture GS-CarbonPLOT 1. Methane 30 m x 0.32 mm I.D., 1.5 µm 2. Acetylene Carrier: He @ 30 cm/s 3. Propane Oven: 125°C for 2 min 5 4. iso-Butane 125°C to 350°C at 20°/min 5. n-Butane Injector: Split 1:20, 250°C 3 Detector: MSD, SIM 6. iso-Pentane 7. n-Pentane 4 1 2 7 6 0 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 Dial 1-816-650-0621 for e-Seminar Audio Permanent Gases Column: GS-CarbonPLOT 30 m x 0.32 mm I.D. x 3.0 µm J&W P/N: 113-3133 Carrier: Helium at 27 cm/sec (calculated off N2 at 35°C) Oven: 35°C isothermal Injector: 185°C, 1:30 split, 250 µL injection volume Detector: TCD, 150°C 1 1. Nitrogen and Oxygen (5% each) 2. Carbon monoxide (5%) 2 3. Methane (4%) 4. Carbon dioxide (5%) 3 4 5 2.0 2.5 3.0 3.5 4.0 & Dial 1-816-650-0621 for e-Seminar Audio Solvents 1. Methylene Chloride GS-CarbonPLOT 2. Acetone 30 m x 0.32 mm I.D., 1.5 µm 3. Carbon Disulfide Carrier: He @ 30 cm/s 3 Oven: 125°C for 2 min 4. Ethyl Ether 125°C to 350°C at 20°/min 5. Ethyl Acetate Injector: Split 1:20, 250°C 6. Benzene Detector: MSD, SIM 6 5 1 2 4 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 Dial 1-816-650-0621 for e-Seminar Audio GS-CarbonPLOT • 0.32 and 0.53 mm ID • 15, 30 and 60 meters • 0.32 mm ID available in thin and thick film • Upper temperature limit of 350º/360ºC Dial 1-816-650-0621 for e-Seminar Audio Break Number 2 For Questions and Answers Press *1 on Your Phone to Ask a Question Dial 1-816-650-0621 for e-Seminar Audio Porous Polymer Phases • Retention is a combination of size and surface interactions between the analyte and the porous solid phase. • The polymers are generally homopolymers of divinylbenzene and divinyl-styrene. • N, R, Q, T, U phases Dial 1-816-650-0621 for e-Seminar Audio Agilent Porous Polymer PLOT Columns • HP PLOT-Q • Bonded polystyrene-divinylbenzene • HP PLOT-U • Bonded divinylbenzene/ethylene glycol dimethacrylate • More polar than “Q” Dial 1-816-650-0621 for e-Seminar Audio Dial 1-816-650-0621 for e-Seminar Audio Natural Gas on HP-PLOT Q Dial 1-816-650-0621 for e-Seminar Audio HP-PLOT Q Volatile Solvents Dial 1-816-650-0621 for e-Seminar Audio HP-PLOT Q Consecutive runs for up to 200 headspace injections of alcohol mixture. Excellent stability!! Dial 1-816-650-0621 for e-Seminar Audio HP-PLOT Q After 150 consecutive direct water injections Dial 1-816-650-0621 for e-Seminar Audio HP-PLOT U Volatile Solvents Dial 1-816-650-0621 for e-Seminar Audio HP-PLOT U Impurities in Acetic Acid Dial 1-816-650-0621 for e-Seminar Audio HP-PLOT U Volatile Primary Amines Dial 1-816-650-0621 for e-Seminar Audio Porous Polymer Column Dimensions Available • Both HP-PLOT Q and HP-PLOT U: • 0.32 and 0.53 mm ID • 15 and 30 meter lengths Dial 1-816-650-0621 for e-Seminar Audio GS-GasPro • Silica-based PLOT column • Bonded stationary phase • Unique selectivity • Highly inert to reactive compounds • Retention stability unaffected by water Dial 1-816-650-0621 for e-Seminar Audio GS-GasPro • Upper temperature limit of 260º/300ºC • No particle generation • Applications •CO, CO2 •C1 to C12 hydrocarbons • trace sulfur analysis • hydrides (arsine, phosphine, germane, etc.) • halocarbons • HCl, NH3 Dial 1-816-650-0621 for e-Seminar Audio Dial 1-816-650-0621 for e-Seminar Audio Dial 1-816-650-0621 for e-Seminar Audio Dial 1-816-650-0621 for e-Seminar Audio Dial 1-816-650-0621 for e-Seminar Audio Dial 1-816-650-0621 for e-Seminar Audio Dial 1-816-650-0621 for e-Seminar Audio Dial 1-816-650-0621 for e-Seminar Audio GS-GasPro Dimensions Available • Currently only available in 0.32 mm ID • 5, 15, 30 and 60 meter lengths Dial 1-816-650-0621 for e-Seminar Audio Considerations for PLOT Column Analysis • Inlet issues • split versus direct injection • gas sampling valves • low dead volume • column ID and flow rate • Detector issues • particle generation or “spiking”; particle traps • column ID and flow rate Dial 1-816-650-0621 for e-Seminar Audio Considerations for PLOT Column Analysis • Column issues • selectivity • capacity; overloaded peaks • inertness • temperature limits • Column contamination • efficiency loss; “ghost peaks”; increase in bleed • water, CO2, high molecular weight hydrocarbons? •Carrier gas purifiers Dial 1-816-650-0621 for e-Seminar Audio Wrap-up E-Seminar Questions Thank you for attending Agilent e-Seminars.