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Principles of Instrumental Analysis

Chapter 27 Gas Chromatography

Gas Chromatography (GC): vaporized analytes (solutes) are partitioned between a mobile gaseous phase and a liquid or a solid stationary phase held in a column. The mobile phase does not interact with molecules of the analytes (solutes). Gas-Liquid Chromatography (GLC): partition between mobile phase and liquid phase immobilized on the surface of an inert solid packing or on the walls of a capillary tubing. Gas-Solid Chromatography (GSC): physical adsorption

27A Principles of GLC

Due to compressibility of gaseous mobile phases, the mathematical relationships obtained in Chapter 26 need minor modification. Retention volume (Vg) instead of retention time (tR): Vg = (K/S) x (273/Tc) Tc : column temperature S : density of liquid stationary phase

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VR = tRF, VM = tMF F: average volumetric flow rate F = Fm x (Tc/T) x (P - PH2O)/P Tc: column temperature (ambient) P: gas pressure at column end (ambient) PH2O: vapor pressure of water Corrected retention volume: VR0 = jtRF, F VM0 = jtMF j: compressibility factor .. (27-4) (27 4) Specific retention volume: Vg = (VR0 - VM0)/mS x 273/Tc = jF(tR tM)/mS x 273/Tc mS: mass of the stationary phase Vg = jFtMk/mS x 273/Tc retention factor k = (tR - tM)/tM = VM0k/mS x 273/Tc = KVS/mS x 273/Tc k = KVS/VM (K: distribution constant) S = mS/VS Vg = K/S x 273/Tc (from eq. 27-4) At a given temperature, Vg depends only on the distribution constant (K) and density (S) of stationary phase (liquid).

van Deemter plot

FIGURE 26-8 Effect of mobile-phase flow rate on plate height for (a) LC and (b) GC. Note very different flow rate and plate height scales.

1) The minimum for LC usually occurs at flow rates well below those for GC. 2) Plates heights (H) for LC columns are an order of magnitude or more smaller than those encountered with GC columns.

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27B Instruments for GLC

FIGURE 2727-1 Block diagram of a typical gas chromatograph. FIGURE 2727-2 A soap-bubble flow meter.

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FIGURE 2727-3 A set of micro-syringes for sample injection.

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FIGURE 2727-4 Cross-sectional view of a microflash vaporizer direct injector.

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Gas sampling valve for quantitative work.

FIGURE 2727-5 A rotary sample valve: valve position (a) is for filling the sample loop ACB; position (b) if for introduction of sample into column.

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Column configuration: constructed of fused silica or stainless steel; formed as coils (diameter: 10~30 cm); housed in a thermostatted oven. Packed column: 1~5 m. Open tubular (capillary) column: ~100 m.

Column temperature p is an important p variable: equal or slightly above the average boiling point of a sample reasonable elution time (2-30 min). In general, optimal resolution is associated with minimal temperature; the cost of lowered temperature is an increase in elution time [Figure 27-7(a)-(b)].

FIGURE 2727-6 Fused-silica capillary columns.

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FIGURE 2727-7 Effect of temperature on gas chromatograms: (a) isothermal at 45; (b) isothermal at 145; (c) programmed at 30 to 180.

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Characteristics of the ideal detectors: 1) Adequate sensitivity. 2) Good stability and reproducibility. 3) A linear responses to solutes (several orders of magnitude). 4) A temperature range from r.t. to at least 400oC. 5) A short response time independent of flow rate. 6) ) High g reliability y and ease of use. 7) Similarity in response toward all solutes. 8) The detector should be non-destructive. TABLE 2727-1 Typical Gas Chromatographic Detectors

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FID responds to number of carbon atom: A mass-sensitive rather than concentration-sensitive. Suitable for organic samples: Functional groups (carbonyl, alcohol, halogen, and amine) yield fewer ions or none at all in a flame. Insensitive to non-combustible gases (H2O, CO2, SO2, CO, noble gases, and NOx) Sensitivity: ~10-13 g/s. Linear response range: ~107 Low noise. Disadvantages: destructive FIGURE 2727-8 A typical flame ionization detector (FID).

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Thermal Conductivity Detector (TCD): Temperature at constant electrical power depends on the thermal conductivity of the surrounding gas. Suitable to both organic and inorganic species. Simplicity & non-destructive. Low sensitivity: ~10-8 g/s. Linear response range: ~105

FIGURE 2727-9 Schematic of (a) a TCD cell, and (b) an arrangement of two sample detector cells and two reference detector cells.

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Nickel-63

FIGURE 2727-10 Schematic diagram of an Electron-Capture Detector (ECD).

Electronegative functional groups tend to capture electrons decrease c rrent Selecti current. Selectively el responds to halogen-containing halogen containing organic compounds: compo nds for detection of environmental samples: pesticides, polychlorinated biphenyls. Selective in response: high sensitivity to halogens, peroxides, quinones, and nitro groups; insensitive to amines, alcohols, and hydrocarbons.

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FIGURE 2727-11 Diagram of a Hall electrolytic conductivity detector.

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AED is an element-selective detector. FIGURE 2727-12. An Atomic Emission Detector (AED) for GC.

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FIGURE 2727-13(a). Chromatogram for a gasoline sample containing a small amount of MTBE and several aliphatic alcohols: monitoring a carbon emission line.

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FIGURE 2727-13(b) Chromatogram for a gasoline sample containing a small amount of MTBE and several aliphatic alcohols: monitoring an oxygen emission line.
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Mass Spectrometry Detectors

FIGURE 2727-14 Schematic of a typical capillary GC/MS system. The effluent from the GC is passed into the inlet of the mass spectrometer, where the molecules in the gas are fragmented, ionized, analyzed, and detected.

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Time, min

FIGURE 2727-15(a). ( ) Typical yp outputs p for a GC/MS system. y In ( (a), ), the total ion (current) chromatogram were 1, N-nitrosodimethylamine, 2, bis(2chloroethyl)ether, 3, bis(2-chloroisopropyl)ether, 4, N-nitrosodi-n-propylamine, and 5, bis(2-chloroethoxy)methane.

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m/z 74

FIGURE 2727-15(b) Typical outputs for a GC/MS system. In (b), the mass chromatogram at m/z = 74 is shown. The peak is due to the parent ion of n-nitrosodimenthylamine (C2H6N2O).

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m/z 93

FIGURE 2727-15(c). Typical outputs for a GC/MS system. A selected selected-ion ion chromatogram m/z = 93 is shown in (c). Peaks 2 and 5 give a response at this m/z value due to fragmentation products.

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27C GC Columns and Stationary Phases

TABLE 27 27-2 Properties and Characteristics of Typical GC Columns

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FIGURE 2727-16 A photomicrograph of a diatomaceous earth (). Magnification 5000X.

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Adsorption on Column Packings or Capillary Walls:

Polar silanol

silanization

Acid washing before silanization removes metal oxide impurities.

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Stationary phase (immobilized liquid) requires: (1) low volatility, (2) thermal stability, (3) chemical inertness, and (4) solvent characteristics (k and ). TABLE 2727-3. Some Common Liquid Stationary Phases for GLC

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Liquid Stationary Phase fro GLC

Polarity Hydrocarbon Polysiloxane R= methyl: Polydimethyl siloxane R= methyl, phenyl: x% Phenyl-polydimethyl siloxane R= methyl, trifluoropropyl: x% Trifluoropropyl-polydimethyl siloxane R= methyl, cyanopropyl: x% Cyanopropyl-polydimethyl siloxane Polyethylene glycol: H-(OCH2CH2)n-OH Polyester: H-(O-RO-CO-R-CO)n-OH Analytes y : Polar: alcohols, acids, amines. Medium polar: ethers, ketones, aldehydes. Non-polar: saturated hydrocarbons. The polarity of the stationary phase should match that of the analytes. When the match is good, the elution order is determined by the boiling point of the analytes
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FIGURE 2727-17(a) 17(a)-(c) Typical chromatograms from open tubular columns coated with (a) polydimethyl siloxane; (b) 5% (phenyl methyldimethyl) siloxane; (c) 50% (phenyl methyldimethyl) siloxane.

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FIGURE 2727-17(d) 17(d)-(f) (d) 50% poly (trifluoropropyl-dimethyl) siloxane; (e) polyethylene glycol; (f) 50% poly (cyanopropyl-dimethyl) siloxane.

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Chiral Stationary Phases (CSP): chiral liquid as stationary phase for separation of enantiomers.
Thalidomide was sold in a number of countries across the world from 1957 until 1961 when it was withdrawn from the market after being found to be a cause of birth defects in what has been called "one of the biggest medical tragedies of modern times".[4It is not known exactly how many worldwide victims of the drug there have been, been although estimates range from 10 10,000 000 to 20,000. 20 000 [5]

(S)-thalidomide

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27D Applications of GC
1) Perform separations 2) Analysis: a) Qualitative analysis: retention times or volumes volumes. * Selectivity factors: * The Retention Index (I): The retention index scale is based on normal alkanes: 100 x no. carbon. b) Quantitative analysis: peak heights or areas.

FIGURE 2727-18 Graphical illustration of the method for determining retention indexes for three compounds. Stationary phase: squalane. Temperature: 60. Retention indexes for normal alkane standards nonane and hexane are Indicated.

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27E Advances in GC
1) High-speed GC 2) Miniaturized GC Systems

FIGURE 2727-19 High-speed chromatogram obtained with isothermal operation (30) for 27 s followed by a 35/min temperature ramp to 90.
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FIGURE 2727-20 Microfabricated columns (a) and chromatogram (b). The columns in (a) were 0.9-m-long spiral and serpentine channels.

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FIGURE 2727-20(b) The mixture (b) was 1, acetone; 2, 2-butanone; 3, benzene; 4, trichloroethylene; 5, 2,5-dimethyl-furan; and 6, toluene. Air was used as the carrier gas with an outlet pressure of 0.5 atm.

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27F Gas-Solid Chromatography (GSC): physical adsorption

packed or (porous-layer) open tubular columns (PLOT) 1) Molecular Sieves: aluminum silicates 2) Porous polymers: cross-linked polystyrenes

FIGURE 2727-21 Typical gas-solid chromatographic separations: (a) a 5 ft. 1/8 in. molecular sieve column; (b) a 30 m 0.53 mm PLOT column. Cn = hydrocarbon with n carbons.
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