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Gas Chromatography

General Design of a GC

Some of the designdetails


Gas supplies usually have either in-line or instrument mounted traps to remove any water, oxygen, hydrocarbons or other contaminants from compressed gases Instruments can have multiple injectors, detectors or columns Injectors and detectors usually have their own temperature controlled zones (small heaters) The GC oven has a large fan and a vent door to help with rapid cooling of the oven Data collection (and integration) can be done using a chart recorder, integrator or a computerized data system

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

The Objective in Chromatography (all types)

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

GC Columns (concentrating on open-tubular capillary columns)

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.

Capillary Column Stationary Phases

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!

For capillary GC columns.


Increased length = greater N, therefore a greater R
expense is possible band broadening if analytes are on the column too long! Increased length leads to longer separations. Do you have the time?

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

Is the column compatible with the detector?


Thick stationary phases bleed more and will contaminate a mass spectrometer.

For most analytical work, a best compromise column is chosen and other variables (temp, etc.) are altered to optimize the separation.

Capillary vs. Packed Columns


Capillary Columns: Packed Columns
Greater sample capacity Lower cost (can make your own) More rugged Most common in process labs or separating/determining major components in a sample (prep GC) Limited lengths reduces R and N Not compatible with some GC detectors Higher resolution (R) Greater HETP and N Shorter analysis time Greater sensitivity Most common in analytical laboratory GC instruments Smaller sample capacity Higher cost/column Columns more susceptible to damage

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!

The traps of temperature


If your temperature at a given time is too high, you can cause the peaks to co-elute
poor resolution vs but a faster 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

You have to choose a compromise temperature program

GC Carrier Gases (the mobile phase)


Usually inert gases (dont react with analytes except sometimes in the detector) Purpose:
sweep sample through the column protect column from oxygen exposure at temperature assist with function of the detector

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

Many different (mostly proprietary) materials


red rubber (bleeds at about 250 C) Thermogreen (good up to about 300 C) High-temperature blue (good a little over 300 C)

The injector is usually lined with a de-activated glass liner


prevents metal injector-sample reactions that would alter analytes or damage the metal of the injector Can be cleaned/replaced regularly

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

Not good for analytes with a wide range of boiling points


some may be swept out the split vent before they are volatilized

Modern capillary GCs come with a Split/Splitless injectors standard


you switch between modes by changing the split vent gas flow and using a different injection liner.

Dont Forget SPME (Solid Phase Microextraction)

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!

Should have a known linear range


if the detector response is very linear, you can use a response factor instead of a calibration curve for quantitation!

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!

Thermal Conductivity (TCD)

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