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POLYSILOXANES Functional Groups

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Presentation on theme: "POLYSILOXANES Functional Groups"— Presentation transcript:

1 POLYSILOXANES Functional Groups
Si O R R Name CH 3 Methyl Phenyl Cyanopropyl CH 2 CN CH 2 CF 3 Trifluoropropyl

2 STATIONARY PHASE % Substitution
% = # of sites on silicon atoms occupied Balance is methyl

3 STATIONARY PHASE Polysiloxanes Methyl Substituted
CH 3 n Si O 100 % methyl (DB-1)

4 POLYSILOXANES Phenyl methyl Substituted
3 CH m n Si O 5% phenyl (DB-5) 35% phenyl (DB-35) 50% phenyl (DB-17)

5 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

6 POLYSILOXANES Cyanopropyl methyl Substituted
CH 3 C H 6 CN m n Si O 50% cyanopropyl (DB-23)

7 POLYSILOXANES Cyanopropylphenyl methyl Substituted
3 H 6 CN n m Si O 6% cyanopropylphenyl (DB-1301) 14% cyanopropylphenyl (DB-1701) 50% cyanopropylphenyl (DB-225)

8 STATIONARY PHASE Poly(ethylene) Glycol
HO CH 2 CH O H n 100% PEG (DB-WAX) Less stable than polysiloxanes Unique separation characteristics

9 SELECTIVITY VS. POLARITY
Selectivity: Solute interactions and separations Polarity: Physical characteristic of the stationary phase

10 POLARITY Nonpolar 100% Methyl (DB-1) 5% Phenyl (DB-5)

11 POLARITY Intermediate
35% Phenyl (DB-35) 50% Phenyl (DB-17) 6% Cyanopropylphenyl (DB-1301) 14% Cyanopropylphenyl (DB-1701)

12 POLARITY Polar 50% Cyanopropylphenyl (DB-225) 50% Cyanopropyl (DB-23)
50% Trifluoropropyl (DB-210) Poly(ethylene) glycol (DB-WAX)

13 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

14 SELECTIVITY Interaction Strengths
Phase Dipersion Dipole H Bonding Methyl Strong None Phenyl Weak Cyanopropyl Moderate Trifluoropropyl PEG

15 DISPERSION INTERACTION Kcal/mole
2 4 6 8 10 Benzene Phenol C10 C12 8.1 11.9 10.9 DB-1 (non-polar)

16 DIPOLE INTERACTION Compounds With Dipole Differences
C=C Cl H C=C Cl H 1,2-dichloroethylene 1,1-dichloroethylene

17 SELECTIVITY Interaction Strengths
Phase Dipersion Dipole H Bonding Methyl Strong None Phenyl Weak Cyanopropyl Moderate Trifluoropropyl PEG

18 COMPOUNDS Properties Compounds Polar Aromatic Hydrogen Bonding Dipole
Toluene no yes induced Hexanol Phenol Decane Naphthalene Dodecane

19 100% 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

20 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

21 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

22 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

23 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

24 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

25 100% 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

26 COLUMN DIAMETER Capillary Columns
I.D. (mm) Common Name 0.53 Megabore 0.45 High speed Megabore 0.32 Wide Narrow 0.18 Minibore

27 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

28 COLUMN DIAMETER Resolution 180°C isothermal
0.53 mm 0.32 mm Square root of resolution is inversely proportional to column diameter

29 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

30 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

31 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)

32 COLUMN LENGTH Most common: meters Available: meters

33 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

34 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

35 FILM THICKNESS Most common: um Available: um

36 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

37 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

38 FILM THICKNESS Resolution
d f When solute k > 5 When solute k < 5

39 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

40 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

41 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.

42 FILM THICKNESS Bleed More stationary phase = More degradation products

43 FILM THICKNESS Inertness Summary
0.25 1.0 3.0 active inactive active inactive active inactive

44 COLUMN DIMENSIONS Diameter Summary
To Increase Make Diameter Resolution Smaller Retention Pressure Flow rate Larger Capacity

45 COLUMN DIMENSIONS Length Summary
To Increase Make Length Resolution Longer Retention Pressure Cost

46 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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