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General Design of a GC
Separation Processes in GC
The analyte is in the gas phase in the GC and partitions between the mobile phase (carrier gas) and the liquid stationary phase that is coated on the inside of an open-tubular capillary column or on particles inside a packed column
Some packed-column GC uses non-coated solid stationary phases, in which case one is performing gas-solid adsorption chromatography
Capillary, open-tubular (WCOT specifically) column GC is the primary type of GC used in quantitative analysis:
higher resolution = greater ability to discriminate between components smaller capacity of the column is not important as long as sufficient analyte is available for detection pg/mL (ppt) to g/mL (ppm) concentration range for liquid analytes
Separate your analytes in the shortest amount of time possible and detect them. How can we do this in GC?
Use different columns for different analyte types
stationary phase diameter of column, stationary phase thickness column length
Use different injection types/temperatures to optimize the process of loading the sample on the column Use different temperature (or pressure) programs for the column Select and use a detector that is suitable for the analyte(s) of interest
Column frame constructed of fused silica tubing Polyamide coating on the outside gives it strength Liquid stationary phases coated or bonded to the inside of the tubing 0.1 - 0.53 mm + ID, 5-100 meters in length, stationary phases usually 0.10 to 1.5 m in thickness Mounted on a wire cage to make them easier to handle 5-150 meters long.
Choosing a GC Column
Is the column compatible with your analytes
polar analytes require polar stationary phases so they will spend some of their time in the stationary phase non-polar analytes require non-polar stationary phases You usually have to compromise on the stationary phase to get a good column for your analytes (which are probably a mix of polar and non-polar) DB-5, HP-5, EC-5, RTX-5 (5% dimethyl, 95% diphenyl polysiloxane) most common general use column.
Temperature range, solvent and carrier gas compatibility Sample capacity versus resolution
usually determines packed vs.. capillary GCs usually setup for either packed or capillary
Lets say you choose a capillary column, theres more to think about!
Increased stationary phase thickness and column diameter provides increased sample capacity and can provide increased resolution
tradeoffs are a longer analysis time and more column bleed with thicker stationary phases
For most analytical work, a best compromise column is chosen and other variables (temp, etc.) are altered to optimize the separation.
Temperature Programming in GC
The simplest way to alter the separation in GC is to alter the temperature program in the oven. You can also alter the pressure of the carrier gas, but this is less common (much). Isothermal = constant temperature Gradient = varied temperature
Analytemobilephase Analyte
stationary phase
By altering the temperature, you vary the rate of the reaction for any analyte:
they spend more or less time in the stationary phase the greater the difference in the times between analytes, the better the separation!
If your temperature at a given time is too low, you can get still get a good separation
adequate resolution, but a separation that takes very long
Most common:
Helium (available relatively pure without extensive purification after it leaves a compressed gas cylinder) Nitrogen (usually requires an oxygen and water trap) Hydrogen
normally used only with flame ionization detectors (FID) since the FID needs it as fuel for the flame still rarely used due to safety concerns (and chromatographic ones)
GC Injection.
Samples are injected through a septum:
keeps oxygen out of the column provides a seal to keep the carrier gas pressure up at the head of the column
carrier gas flow rate is determined by the pressure or the gas at the opening of the column
Injection types
On-Column Injection:
used widely in packed-column GC, less in capillary GC sample is deposited directly on the column
Good for thermally unstable compounds Good for quantitative analysis at low concentrations
all sample is available to travel to the detector
BUT, you can inject only a relatively small amount of sample in capillary GC anyhow.
Splitless Injection:
Sample is vaporized in the injector itself and ALL of the sample is swept onto the column by the carrier gas Again, relatively small samples are injected (10 L or less in capillary GC) Sample spends a large amount of time in the injector Best for trace (1 -100 ppm range) concentrations of high boiling point analytes in low boiling point solvents
extra time in the injector helps volatilize the analytes.
Split Injection:
the injection is split, with only a portion of the sample (usually 1% - 20%) actually making it to the column the most common method of injecting samples onto small diameter, open-tubular columns.
Even if you inject 20 L, only a fraction (adjustable) makes it on to the column
GC Detectors
A dozen or more varieties (some obscure) Must be:
sensitive to the analytes of interest compatible with the column, carrier gas, solvent, etc. rugged enough to withstand general unattended used
Ive run our new GC for 36 hours straight without touching it!
Usually require separate gas supplies (other than the carrier gas), have their own temperature control. Measure nothing more than a voltage or a current.
The carrier gas has a known thermal conductivity. As the thermal conductivity of the column eluent (gas flow in) changes, the resistance of the filament changes. The presence of analyte molecules in the carrier gas alter the thermal conductivity of the gas (usually He) There is normally a second filament to act as a reference (the carrier gas is split) Increased sensitivity with decreasing temperature (detector), flow rate and applied current. Filaments will burn out (oxidized) in the presence of oxygen if hot!
Non-destructive
Destructive, sample lost. Analytes containing C burn in a hydrogenoxygen flame and produce ions CHO+ ions are collected on a cathode and the current they produce results in the signal WILL NOT detect non-C containing compounds! Requires H2 supply (tank or generator) and O2 supply (compressed air) H2 carrier gas can be used, eliminating the need for a supply for the detector A makeup gas can also be required!
FID
CH O
H2 , O2 Flame
CHO e
Particularly sensitive to halogens nitriles, carbonyls, nitro compounds Analytes pass through a cell, in which electrons are traveling between a 63Ni electrode and a collector electrode As analytes with electron capturing ability pass through the cell, the flow of electrons is interrupted. The change in current, due to reduced flow of electrons, is recorded. EXTREMELY SENSITIVE TO HALOGENS
could ruin detector with 1 ppm hexachlorocyclohexane by contaminating it with excess analyte
ECD
Widely used for the determination of pesticides, herbicides and PCBs in environmental samples. Non-destructive