Choosing the Best Column for Your Analysis

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Typical Gas Chromatographic System

Mol-Sieve Traps Fixed Restrictors

Regulators Flow Controller

Injection Port

Detector

Electrometer

Recorder/ Integrator Column

Hydrogen

Cylinders or Generators

Carrier Gas

Air

The optimal column will give the greatest resolution in the shortest analysis time.

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Stationary Phase Polymers

R = methyl, phenyl, cyanopropyl, trifluoropropyl Siloxane

Siarylene backbone

H H HO - - C-C-O H H -H n

Polyethylene glycol backbone

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Capillary Column Types

Porous Layer Open Tube (PLOT)
Solid Particles Carrier Gas

Wall Coated Open Tube (WCOT)

Carrier Gas

Liquid Phase

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WCOT Column Types

Agilent J&W has over 50 different stationary phase offerings

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FactorFourTM Phases
VF-1ms, VF-5ms, VF-5ht, VF-5ht UltiMetal VF-17ms, VF-17ms for PAH, VF-35ms, VF-200ms,VF-Xms, VF-23ms, VF-624ms, VF-DA, VF-1301ms, VF-Pesticides, VF-1701ms, VF-WAXms

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20+ Different Specialty Phases

Specialty phases are columns that are optimized to perform a specialized GC analysis. Column Typical Application DB-624 EPA and USP volatiles DB-VRX volatiles analysis HP-VOC volatiles analysis DB-502.2 EPA Method 502.2 DB-5.625 EPA semi-volatiles analysis DB-608 EPA Method 608 DB-1701P EPA pesticides analysis DB-MTBE total petroleum hydrocarbon (TPH) HP-PONA petroleum hydrocarbon analysis DB-HT SimDis hi-temp simulated distillation DB-ALC1 & ALC2 blood alcohol analysis HP-88 fatty acid methyl ester (FAME)

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Select TM Column Examples

Environmental applications CP-Sil 88 for dioxins, Select mineral oil, CP-Select 624 CB Chiral applications CP-Chirasil Val, CP-Chirasil-DEX CB Chemical applications CP-Volamine, CP-Select CB for MTBE, CP-PONA C8, CP-Propox, Select Silanes, CP-SimDist UltiMetal TM , CP-Lowox TM Food and Beverage applications CP-Carbowax 400, Select FAME, CP-Sil 88 for FAME, CP-FFAP

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PLOT Column Types

PLOT columns are primarily, but not exclusively, used for the analysis of gases and low boiling point solutes (i.e., boiling point of solute is at or below room temperature). Agilent J&W PLOT columns begin with the designation of
GS (Gas Solid) or HP-PLOT followed by a specific name 10 stationary phases

GS-OxyPLOT: oxygenates HP-PLOT Molesieve: O2, N2, CO, Methane HP-PLOT Alumina and GS-Alumina: complex hydrocarbon gas matrices, ethylene and propylene purity, 1,4-butadiene HP-PLOT Q: freons, sulfides HP-PLOT U: C1 to C7 hydrocarbons, CO2, Polar Hydrocarbons GS-GasPro: freons, sulfurs, inorganic gases GS-CarbonPLOT: inorganic and organic gases

GS-OxyPLOT 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

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PLOT GC Columns from Varian Line

Porous Polymers
CP-PoraBOND Q CP-PoraBOND U

Alumina
KCL Na2SO4 MAPD

CP-PoraPLOT Q CP-PoraPLOT U CP-PoraPLOT S CP-PoraPLOT Q-HT CP-PoraPLOT amines

Multi Layer
CP-Lowox

Porous Silica
SilicaPLOT

Graphatised Carbon
CP-CarboPLOT P7 CP-CarboBOND

Zeolites
Molsieve 5A Molsieve 13x

SelectTM permanent gases

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Particle and Bonded PLOT columns

In-situ polymerization process
High mechanical stability No particle loss Increased max. temp. specification
Larger app. range Fast bake-out CP-PoraBOND Q CP-PoraBOND U CP-CarboBOND

5 to 50 um

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Plot Column Utility

Permanent gases Noble gases, O2, N2, H2, CO, CO2, CH4 Light hydrocarbons C1 C8, saturated, unsaturated, aromatics natural gas, C2,C3,C4 streams Volatile sulfur compound H2S, COS, mercaptanes, sulfides, disulfides Oxygenates Alcohols, ketones, ethers Solvents Oxygenates, aromatics, alkanes, chlorinated hydrocarbons. Chlorinated and fluorinated hydrocarbons

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Packed Columns
1950 Introduction with the first gas chromatographs

Packed Column Designs and Materials

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Properties of Chromosorb Support Materials

Chromosorb P for high load: volatiles, light hydrocarbons Chromosorb WHP, T, 750 for max inertness: acids, basics

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Packed Column Comparison with Mega-bore Fused Silica

Robust, virtually unbreakable & bendable
Ideal in complex analyzer constructions with limited spacing

Very high sample load possible, 2 5mL

Trace analyses for ppm gas impurities

Simple sample introduction, direct injection, on-column

Syringe or gas sampling valve Micro-packed columns (0.8mm ID) with high efficiency

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Packed Column Anatomy

Packed Columns
1 12 m length Internal Diameter 0.5 4mm Tubing Stainless Steel, UltimetalTM SS, Glass, Nickel, Teflon Packing Coated packing
Inert, solid support (diatomaceous earth) coated with liquid stationary phase (e.g. OV-1, SE-30, Carbowax 20M, FFAP)

Porous packing
Porous polymers (PoraPak Q, N, HayeSep Q, R, S, etc.) Porous carbons (Carboxens, Carbosieves, Carbotraps)

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Packed Column Utility

Petrochemical & Chemical, main market
Process analyzers Lab based analyzers
Gas analyzers, CO, CO2, PIONA, Refinery gas

ASTM, IP, ISO and UOP methods

E.g.TCEP, DC-200, SE-30, OV-1

Gas analyses
HayeSeps, Carboxens

Micro-GC
Micro-packed columns for Natural Gas modules

Simple chemical purity analyses

Older methods

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Selectivity
Relative spacing of the chromatographic peaks The result of all non-polar, polarizable and polar interactions that cause a stationary phase to be more or less retentive to one analyte than another

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Impact of Efficiency, Selectivity and Retention on Resolution

7.00

Typical Method Development Parameters

6.00

5.00

Resolution

4.00

Increase N Increase Alpha Increase k'

3.00

2.00

1.00

Rs = N /4 (-1)/ k /(k+1)
0.00

Plates: Alpha: k :

5000
1

10000
6

10

15000
11

12

13

14

15

20000
16

17

18

19

20

25000
21

1.10 2.0

1.35 4.5

1.60 7.0

1.85 9.5

2.1 12.0

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Optimizing Selectivity

Match analyte polarity to stationary phase polarity

Like dissolves like (oil and water dont mix)

Take advantage of unique interactions between analyte and stationary phase functional groups

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CLP Pesticides with High Efficiency Columns

2 3 5 7 8 6 4 9 10 12 13 19 14 15 16 18 17 20
2 5 . 0 3 0 . 0 3 5 . 0 4 0 . 0 4 5 . 0 5 0 . 0 5 5 . 0 6 0 . 0 6 5 . 0 7 0 . 0

5989-7616EN

DB-XLB
21 22

11

2 1

5 7

9 10 12 13 11

21 19 14 16 15 17 18 20

DB-17ms
22

6 4

2 5 . 0

3 0 . 0

3 5 . 0

4 0 . 0

4 5 . 0

5 0 . 0

5 5 . 0

6 0 . 0

6 5 . 0

7 0 . 0

Final chromatograms for both the primary and confirmation columns for optimized CLP pesticides analysis.

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PCB Congener Analysis

PCBs PolyChlorinated Biphenyls, a mixture of up to 209 congeners

5989-6095EN

DB-XLB has been shown to provide excellent selectivity for this application. Refer to pages 369-371 of Agilent Consumables Catalog for a list of chromatograms and conditions for PCB applications. 153 Hz
Heart Cutting with the Deans Switch to Isolate Target PCBs from Fish Oil Spiked with Aroclor 1260
Hz

Column 2: DB-200 4000 P/N 122-2033 3500 3000 30m x 0.25mm x 0.5 m
2000

180 138

118

ECD1 A, ECD1A, Front Signal (CHUANHONG FISH OIL DATA JAN 2007\20070122-PCB\PCB02-CALIBRATION IN ISO-OCTANE 2007-01-22 2500

101

Column 1: DB-XLB 350 P/N 121-1232 30m x0.18mm x 01.8m

300

1500 1000 500 4

28
6 8

52

10

12

14

16

18 min

250

200

150

Heart Cuts

28 52

101

10

118 153 138

12

180

14

16

18

min

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Selectivity is important but not everything

High inertness and low bleed can be critical factors in column selection. Temperature limits will play a role as well. These parameters are analyte defined.

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Stationary Phase Bleed

A thermodynamic equilibrium process that occurs to some degree in all columns, and is proportional to the mass amount of stationary phase inside the capillary tubing/carrier gas flow path Polysiloxane backbone releases low molecular weight, cyclic fragments Is negligible in low temperature, O2-free, clean GC systems Increased by increased temperature, oxygen exposure, or chemical damage

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Bleed: Why Does It Happen?

Back Biting Mechanism of Product Formation
H3C CH3 CH3 CH3 CH3 Si O Si O Si O Si O Si CH3 CH3 CH3 CH
3

CH3 Si HO O Si O CH3 CH3 CH3

CH3 CH3

CH3

CH3 CH3 CH3 CH3

Si O Si O Si O Si O Si O Si O Si OH CH3 CH3 CH3 CH3 CH3 CH3 CH3

CH3

CH3 CH3 CH3 CH3 Si O Si O Si O Si OH CH3 CH3 CH3 CH3

H3C CH3 Si O O CH3 Si H3C Si O CH 3 H3C

Cyclic products are thermodynamically more stable!

Repeat

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DB-5ms Structure

O
CH 3

DB-5 Structure

DB-5ms Structure

CH 3

Si CH 3 O Si O CH 3 Si CH 3 O CH 3 Si CH 3
DB-5 5% Phenyl

CH 3 CH 3

Si O
CH 3 CH 3

Si
CH 3

Si
CH 3

O
CH 3

Si
DB-5ms 1.Increased stability 2.Different selectivity 3.Optimized to match DB-5

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Difference in Selectivity
Solid line: DB-5ms 30 m x .25 mm I.D. x .25 m Dashed line:DB-5 30 m x .25 mm I.D. x .25 m Oven: 60o C isothermal Carrier gas: H2 at 40 cm/sec 1: Ethylbenzene 2: m-Xylene 3: p-Xylene 4: o-Xylene

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Four Types Of Low Bleed Phases

Phases tailored to mimic currently existing polymers -Examples: DB-5ms, DB-35ms, DB-17ms, DB-225ms Phases unrelated to any previously existing polymers -Examples: DB-XLB Optimized manufacturing processes -DB-1ms, HP-1ms, HP-5ms Hand selected columns

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Benefits of Low Bleed Phases

PAH Sensitivity Using DB-35MS

Commercially Available 35% phenyl column

Benzo[ghi]perylene S/N = 15

4 2 3 5 6

DB-35MS
7

Benzo[ghi]perylene S/N = 120

15 12 13 14 16

8 9 10

11

1. Naphthalene 2. Acenaphthylene 3. Acenaphthene 4. Fluorene 5. Phenanthrene 6. Anthracene 7. Fluoranthene 8. Pyrene 9. Benz[a]anthracene 10. Chrysene 11. Benzo[b]fluoranthene 12. Benzo[k]fluoranthene 13. Benzo[a]pyrene 14. Indeno[1,2,3,c,d]anthracene 15. Dibenz[a,h]anthracene 16. Benzo[g,h,i]perylene

10

15

20

25

min

Columns: 30 m x 0.32 mm x 0.35 um. Carrier: H2, constant flow, 5 psi at 100 oC. Injector: 275 oC, splitless, 1 ul , 0.5-5ppm. Oven: 100 oC to 250 oC (5 min.) at 15 oC/min.,; then to 320 oC (10 min.) at 7.5 oC/min. Detector: FID, 320 oC.

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Polarity vs Stability/Temperature Range

Polarity

Stability Temperature Range

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Stationary Phase Selection

Existing information Selectivity/Polarity Critical separations Temperature limits Application designed
Examples: DB-VRX, DB-MTBE, DB-TPH, DB-ALC1, DB-ALC2, DB-HTSimDis, DB-Dioxin, HP-VOC, and now SelectTM phases

Choose the column phase that gives the best separation but not at the cost of robustness or ruggedness.

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Column Diameter - Theoretical Efficiency

Total Plates I.D. (mm) 0.05 0.10 0.18 20 m N ~ 112,000 0.20 0.25 30 m N ~ 112,000 0.32 0.45 k=5 0.53 n/m 23,160 11,580 6,660 5830 4630 3660 2840 2060
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5m
10 m

N ~ 112,000 N ~ 112,000

PHASE RATIO ()
Film Thickness

Column Dimensions

Phase Ratio 44 44

30 m x .53 mm x 3.0 m 30 m x .32 mm x 1.8 m KC = k = r 2df

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Different Column I. D.
Equal Phase Ratios
Column : DB-624 30 m, 0.53 mm, 3 m Carrier: Helium, 40 (cm/sec) Oven: 65 C Injection: Split Detector: FID

Column :

DB-624 30 m, 0.32 mm, 1.8 m

10 Time (min)

15

20

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Column Diameter and Capacity

I.D. (mm) 0.05 0.10 0.18 0.20 Like Polarity Phase/Solute 0.25 m film thickness 0.25 0.32 0.45 0.53 Capacity (ng) 1-2 6-13 25-55 35-70 80-160 110-220 600-800 1000-2000
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Column Diameter - Inlet Head Pressures (Helium)

I.D (mm) 0.05 0.10 0.18 0.20 0.25 30 meters Hydrogen pressures x 1/2 0.32 0.45 0.53 Pressure (psig) 275-400 90-130 30-45 25-40 15-25 10-20 3-7 2-4

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Column Diameter and Carrier Gas Flow

Lower flow rates: Smaller diameter columns

Higher flow rates: Larger diameter columns

Low flow rates : GC/MS High flow rates: Headspace, purge & trap

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Diameter Summary

If you decrease the inside diameter: Efficiency Resolution Pressure Capacity Flow rate Increase Increase Increase Decrease Decrease

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Film Thickness and Capacity

Thickness (m) 0.10 0.25 0.50 1 3 5 0.32 mm I.D. Like Polarity Phase/Solute Capacity (ng) 50-100 125-250 250-300 500-1000 1500-3000 2500-5000

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Film Thickness and Bleed

More stationary phase = More degradation products

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Film Thickness and Inertness

0.25 1.0 3.0

active

inactive

active

inactive

active

inactive
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Film Thickness Summary

If you increase the film thickness: Retention Resolution (k<5) Resolution (k>5) Capacity Bleed Inertness Efficiency Increase Increase Decrease Increase Increase Increase Decrease

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Column Length and Resolution

R n L
Length X 4 = Resolution X 2

t L
R=0.84 2.29 min R=1.16 4.82 min R=1.68 8.73 min

15 m

30 m

60 m

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Analysis of Naphtha
Shorter column, Smaller column diameter same phase ratio
Naphtha CP-Sil 5 PONA 250 m x 100 m Df = 0.5m, = 125 4500 P = 45 PSI (315 kPa)
80 min

Same

Similar separation 3 to 4 time faster

CP-Sil 5 PONA 100 m x 40 m Df= 0.2m, =125 500 P = 95 PSI (670 kPa)

20 min

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Length Summary

If you Increase Length: Efficiency Resolution Analysis Time Pressure Cost Increase Increase Increase Increase Increase

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Level of Inertness
Important for active analytes Semi-volatiles Acidic compounds Basic compounds Unknowns that may contain active analytes

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Mexico 2012

High Temperature GC Analysis

Hydrocarbons
Paraffin or hydrocarbon waxes Polywax 655, 1000, 2000 Heavy vacuum residues Crudes, SimDist

Natural waxes
Carnauba wax, Bees wax

Triglycerides
Biodiesel, vegetable oils

Polymer Additives Surfactants

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Critical Parameters in HT GC

Oven Detection
HT FID, MS

Injection
Critical sample introduction Reduce discrimination effects On-column techniques

Column
Tubing material: fused silica/metal Liquid phase temperature robustness

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UltiMetal surface coating and GC Columns

SS tubing 1st layer:: SS surface treatment 2nd layer: Deactivation layer 3rd layer: Liquid phase layer

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UltiMetal, SiO2 Deposition Technology Applied for Packed Columns and 0.53mm Capillary Columns

316 SS tubing 1st layer: SS surface treatment 2nd layer: Deactivation layer

Coated packing

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UltiMetal surface coating

SiO2 Deposition Techniques

Inert coating surface

Inert coating surface Virtually unbreakable Flexible SS tubing Coating of all liquid phases Phase stabilization Low column bleed Coupling issues

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Improved Efficiency and Peakshape

+50%
N-C11 N-C12

n-C13

n-C14

Regular SS

UltiMetal

1m x 1/8 packed column, 5% OV-101 on Chromosorb WAW, 80 - mesh Analysis at 120C

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SimDist Analysis C20 C100

430C

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Phase Degradation on Different Column Surfaces

Column Bleed Characteristics at High Temperature
40 Measured Bleed (pA) 35 30 25 20 15 10 5 0
x x x x x Up to 325 C virtually NO bleeding

Non-polar phase on fused silica PDMS deactivated surface: VF-5ms

Non-polar phase on UltiMetal PDMS deactivated surface: VF-5ht

250 275 300 325 350 375 400 425 450 475 Oven Temperature (C)

UltiMetal seems superior for HT applications

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HT Analysis of Palm Oil

Column: VF-5HT UltiMetal , 30m x 0.25mm x 0.1m

400C

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Polymer Additives
pA 400 350 300 250 200 150 100 50

1. 2. FID1 A, 3. 4. 5. 9.

AO2246 Tinivin 350 (JAN\JN17EB06.D) Cyasorb 5411 Irgafos 16 Tinuvin 234 Oxidized Irgafos 168

1 3 2

VF-5HT Column: WCOT Ulti-Metal VF-5ht-SimDist (Cat. 15m x 15m x 0.25mm x0.1m + 2m RGno. CP9091) 0.25mm x 0.10m (df)
9

PETS release agents

solvent

10 4
5 10 15 20 25 30 35 min

GC-settings:
Mode= constant flow Gas type= Nitrogen Pressure= 4.00 psi Flow= 0.5 ml/min. Average velocity= 16 cm/sec Injection volume= 0.5 l Inlet= cool on-column Detector temp.= 400C Oven program: Oven ramp C/min Initial 40 Ramp 1 40 Ramp 2 10 Run time = 40.00 min. next C Hold min. 2.00 180 0.00 400 12.50

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HT-GC-FID Polymer Additives

Narrow Bore Advantages

Varian Ultimetal, SimDist, 100% PDMS 10m x 0.53mm x 0.07m

400C

Varian Ultimetal, VF-5HT 15m x 0.25mm x 0.1m + 2m 0.53mm Ultimetal RG

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Column Coupling
Factory installed guard columns & retention gaps for 0.53mm, 0.32mm & 0.25mm UltiMetal columns

0.53mm RG

0.25mm / 0.32mm column

Poor & Good Coupling

Ready for use Leak tested Extended column lifetimes

Perfect Chromatography

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UltiMetal column Summary

3 phases for high temperature GC SimDist Select for Biodiesel VF-5ms All Internal diameters 0.25mm 0.32mm 0.53mm Factory installed 0.53mm UltiMetal retention gaps

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Easy ordering Agilent packed columns

Packed Columns Quotation Request Form

UltiMetal option

Infinite number of combinations: Supports Liquid phases Tubing material Tube dimensions Type GC (glass columns) Packed Columns Quotation Request Form simplifies quotation process

Further Options: Preconditioning and testing

Bending Nuts & ferrules choice

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Column Selection Summary

Stationary Phase Type consider polarity and column type Column Internal Diameter- consider speed, inj. volume & cost Stationary Phase Film Thickness- consider retention, capacity and potential for bleed Column Length- consider shortest column for analysis Level of inertness- consider sample activity

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Power of Two
From Agilent J&W
The innovation, quality and products you have come to know including our newest offerings Ultra Inert Column line High efficiency GC column line

From our New Colleagues

The innovation, quality and products you have come to know including some new offerings CP PoraPLOT and CP CarboPLOT columns SelectTM Series UltiMetalTM High temperature columns

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Thank you.

Questions?

GC Method Translation, Theres an App for That.

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Addendum - Optimizing Selectivity

Match analyte polarity to stationary phase polarity

Like dissolves like (oil and water dont mix)

Take advantage of unique interactions between analyte and stationary phase functional groups

Mexico 2012