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POLYSILOXANES Functional Groups
Si O R R Name CH 3 Methyl Phenyl Cyanopropyl CH 2 CN CH 2 CF 3 Trifluoropropyl
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STATIONARY PHASE % Substitution
% = # of sites on silicon atoms occupied Balance is methyl
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STATIONARY PHASE Polysiloxanes Methyl Substituted
CH 3 n Si O 100 % methyl (DB-1)
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POLYSILOXANES Phenyl methyl Substituted
3 CH m n Si O 5% phenyl (DB-5) 35% phenyl (DB-35) 50% phenyl (DB-17)
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DB-5MS Structure O O Si Si CH 3 CH 3 DB-5 Structure DB-5ms Structure
DB-5 5% Phenyl DB-5ms 1.Increased stability 2.Different selectivity 3.Optimized to match DB-5
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POLYSILOXANES Cyanopropyl methyl Substituted
CH 3 C H 6 CN m n Si O 50% cyanopropyl (DB-23)
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POLYSILOXANES Cyanopropylphenyl methyl Substituted
3 H 6 CN n m Si O 6% cyanopropylphenyl (DB-1301) 14% cyanopropylphenyl (DB-1701) 50% cyanopropylphenyl (DB-225)
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STATIONARY PHASE Poly(ethylene) Glycol
HO CH 2 CH O H n 100% PEG (DB-WAX) Less stable than polysiloxanes Unique separation characteristics
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SELECTIVITY VS. POLARITY
Selectivity: Solute interactions and separations Polarity: Physical characteristic of the stationary phase
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POLARITY Nonpolar 100% Methyl (DB-1) 5% Phenyl (DB-5)
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POLARITY Intermediate
35% Phenyl (DB-35) 50% Phenyl (DB-17) 6% Cyanopropylphenyl (DB-1301) 14% Cyanopropylphenyl (DB-1701)
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POLARITY Polar 50% Cyanopropylphenyl (DB-225) 50% Cyanopropyl (DB-23)
50% Trifluoropropyl (DB-210) Poly(ethylene) glycol (DB-WAX)
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POLARITY Solubility And Retention
2 4 6 8 Hexanol C10 C12 100% Methyl (non-polar) 2 4 6 8 C10 C12 Hexanol 100% PEG (polar) 30 m x 0.32 mm ID, 0.25 um He at 35 cm/sec °C at 15°/min
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SELECTIVITY Interaction Strengths
Phase Dipersion Dipole H Bonding Methyl Strong None Phenyl Weak Cyanopropyl Moderate Trifluoropropyl PEG
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DISPERSION INTERACTION Kcal/mole
2 4 6 8 10 Benzene Phenol C10 C12 8.1 11.9 10.9 DB-1 (non-polar)
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DIPOLE INTERACTION Compounds With Dipole Differences
C=C Cl H C=C Cl H 1,2-dichloroethylene 1,1-dichloroethylene
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SELECTIVITY Interaction Strengths
Phase Dipersion Dipole H Bonding Methyl Strong None Phenyl Weak Cyanopropyl Moderate Trifluoropropyl PEG
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COMPOUNDS Properties Compounds Polar Aromatic Hydrogen Bonding Dipole
Toluene no yes induced Hexanol Phenol Decane Naphthalene Dodecane
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100% METHYL POLYSILOXANE 2 4 6 8 10 12 14 16 1 3 5 1. Toluene 2. Hexanol 3. Phenol 4. Decane (C10) 5. Naphthalene 6. Dodecane (C12) Strong Dispersion No Dipole No H Bonding
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5% PHENYL 2 4 6 8 10 12 14 16 5% Phenyl 1 3 5,6 1. Toluene 2. Hexanol 3. Phenol 4. Decane (C10) 5. Naphthalene 6. Dodecane (C12) 2 4 6 8 10 12 14 16 100% Methyl 1 3 5 Strong Dispersion No Dipole Weak H Bonding
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50% PHENYL 100% Methyl 2 4 6 8 10 12 14 16 1 3 5 50% Phenyl 1. Toluene 2. Hexanol 3. Phenol 4. Decane (C10) 5. Naphthalene 6. Dodecane (C12) Strong Dispersion No Dipole Weak H Bonding
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50% CYANOPROPYL 1. Toluene 2. Hexanol 3. Phenol 4. Decane (C10) 5. Naphthalene 6. Dodecane (C12) 2 4 6 8 10 12 14 16 1 5 3 50% Cyanopropyl Strong Dispersion Strong Dipole Moderate H Bonding 2 4 6 8 10 12 14 16 100% Methyl 1 3 5
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14% CYANOPROPYLPHENYL 1. Toluene 2. Hexanol 3. Phenol 4. Decane (C10) 5. Naphthalene 6. Dodecane (C12) 2 4 6 8 10 12 14 16 1 3 5 14% Cyano- propylphenyl 2 Strong Dispersion None/Strong Dipole (Ph/CNPr) Weak/Moderate H Bonding (Ph/CNPr) 4 6 8 10 12 14 16 100% Methyl 1 3 5
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50% CYANOPROPYLPHENYL 1. Toluene 2. Hexanol 3. Phenol 4. Decane (C10) 5. Naphthalene 6. Dodecane (C12) 2 4 6 8 10 12 14 16 1 5 3 50% Cyano- propylphenyl Strong Dispersion None/Strong Dipole (Ph/CNPr) Weak/Moderate H Bonding (Ph/CNPr) 2 4 6 8 10 12 14 16 100% Methyl 1 3 5
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100% POLYETHYLENE GLYCOL 2 4 6 8 10 12 14 16 1 5 3 100% PEG 1. Toluene 2. Hexanol 3. Phenol 4. Decane (C10) 5. Naphthalene 6. Dodecane (C12) Strong Dispersion Strong Dipole Moderate H Bonding 2 4 6 8 10 12 14 16 100% Methyl 1 3 5
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COLUMN DIAMETER Capillary Columns
I.D. (mm) Common Name 0.53 Megabore 0.45 High speed Megabore 0.32 Wide Narrow 0.18 Minibore
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COLUMN DIAMETER Inlet Head Pressures Helium
I.D (mm) Pressure (psig) 0.10 0.20 25-35 0.25 15-25 0.32 10-20 0.53 2-4 30 meters Hydrogen pressures x 1/2
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COLUMN DIAMETER Resolution 180°C isothermal
0.53 mm 0.32 mm Square root of resolution is inversely proportional to column diameter
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COLUMN DIAMETER Retention 80°C isothermal
21.81 0.25 mm 5 10 15 20 16.06 0.32 mm 2 4 6 8 10 12 14 16 Isothermal: Retention is inversely proportional to column diameter Temperature program: 1/3-1/2 of isothermal values
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COLUMN DIAMETER Capacity Like Polarity Phase/Solute
I.D. (mm) Capacity (ng) 0.20 50-100 0.25 75-150 0.32 0.53 0.25 um film thickness
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COLUMN DIAMETER Carrier Gas Flow Rate
Smaller diameters for low flow situations (e.g., GC/MS) Larger diameters for high flow situations (e.g., purge & trap, headspace)
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COLUMN LENGTH Most common: meters Available: meters
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COLUMN LENGTH Resolution and Retention 210°C isothermal
2.29 min R=1.16 4.82 min R=1.68 8.73 min 15 m 30 m 60 m Square root of resolution is inversely proportional to length Isothermal: Retention is proportional to length Temperature program: 1/3-1/2 of isothermal values
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COLUMN LENGTH Inlet Head Pressures Helium
Length (m) Pressure (psig) 15 8-12 30 15-25 60 30-45 0.25 mm I.D. Hydrogen pressures x 1/2
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FILM THICKNESS Most common: um Available: um
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FILM THICKNESS Retention 100°C Isothermal
2 4 6 8 7.00 0.25 um 5 10 15 20 25 24.59 1.00 um Isothermal: Retention is proportional to film thickness Temperature program: 1/3-1/2 of isothermal values
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FILM THICKNESS Equal Retention: Isothermal
2 4 6 8 7.00 0.25 um 100°C 1.00 um 2 4 6 8 7.08 137°C DB-1, 30 m x 0.32 mm ID He at 37 cm/sec C10, C11, C12
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FILM THICKNESS Resolution
d f When solute k > 5 When solute k < 5
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FILM THICKNESS Resolution at Low k
1.2 1.4 1.6 1.8 2 3 4 6 0.25 um 1.00 um 3.00 um 2.0 min 3.5 min 6.5 min DB-1, 30 m x 0.32 mm ID 40°C isothermal, He at 35 cm/sec Solvent mixture
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FILM THICKNESS Resolution at High k
R = 0 k = 0.09 1.900 2.000 2.100 2.200 3.6 3.8 4.0 4.2 4.4 4.6 4.8 5.0 R = 0.81 k = 2.55 R = k = 13.46 5.00 um 10 12 14 16 18 0.25 um 1.00 um 2.2 min 5.0 min 18.0 min DB-1, 30 m x 0.32 mm ID 40°C isothermal, He at 35 cm/sec Solvent mixture
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FILM THICKNESS Capacity Like Polarity Phase/Solute
Thickness (um) Capacity (ng) 0.10 50-100 0.25 1.0 3.0 5.0 0.32 mm I.D.
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FILM THICKNESS Bleed More stationary phase = More degradation products
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FILM THICKNESS Inertness Summary
0.25 1.0 3.0 active inactive active inactive active inactive
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COLUMN DIMENSIONS Diameter Summary
To Increase Make Diameter Resolution Smaller Retention Pressure Flow rate Larger Capacity
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COLUMN DIMENSIONS Length Summary
To Increase Make Length Resolution Longer Retention Pressure Cost
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COLUMN DIMENSION Film Thickness Summary
To Increase Make Film Retention Thicker Resolution (k<5) Resolution (k>5) Thinner Capacity Bleed Inertness
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