GC Instruments

Carrier gas: He (common), N2, H2

Pinlet 10-50 psig
Flow = 25-150 mL/min packed column
Flow = 1-25 mL/min open tubular column
Column: 2-50 m coiled stainless steel/glass/Teflon
Oven: 0-400 °C ~ average boiling point of sample
Accurate to <1 °C
Detectors: FID, TCD, ECD, (MS)
 GC Carrier Gases (the mobile phase)
• Usually “inert” gases (don’t 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)
 INJECTION PORT
• 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
 Typical Injection Applications
• Split - default, conc. samples (>0.1%), sample
size of 1 uL or less, 0.2-2% of sample on
column
• Splitless – dilute samples (<0.01%), 80% of
sample on column
• On Column – easily decomposed samples,
100% of sample on column
• 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.
 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
– GC’s usually setup for either packed or capillary
 Capillary vs. Packed Columns
• Capillary Columns: • Packed Columns
– Higher resolution (R) – Greater sample capacity
– Greater HETP and N – Lower cost (can make your own)
– Shorter analysis time – More rugged
– Greater sensitivity – Most common in process labs or
– Most common in analytical separating/determining major
laboratory GC instruments components in a sample (prep GC)
– Smaller sample capacity – Limited lengths reduces R and N
– Higher cost/column – Not compatible with some GC
detectors
– Columns more susceptible to
damage
 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.
 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

Analyte mobile phase  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
DETECTOR
 GC Detectors
The following devices are common types of GC detectors:
1. Thermal Conductivity Detector (TCD)
2. Flame Ionization Detector (FID)
3. Nitrogen-phosphorus Detector
4. Electron Capture Detector (ECD)
5. Mass Spectrometers (discussed later in the course)

The choice of detector will depend on the analyte and how the GC method is
being used (i.e., analytical or preparative scale)
 1.) Thermal Conductivity Detector
(TCD)
- katherometer or hot-wire detector
- first universal detector developed for GC

Process
- measures a bulk property of the mobile phase leaving the column.
- measures ability to conduct heat away from a hot-wire (i.e., thermal conductivity)
- thermal conductivity changes with presence of other components in the mobile
phase

Considerations
- mobile phase must have very different thermal conductivity then solutes being
separated.
- most compounds separated in GC have thermal conductivity of about 1-4X10-5.
- H2 and He are carrier gases with significantly different thermal conductivity values.
- H2 reacts with metal oxides present on the resistors, so not used
Design
- based on electronic circuit known as a
Wheatstone bridge.
- circuit consists of an arrangement of four
resistors with a fixed current applied to them.
- thermal conductivity changes with presence of
other components in the mobile phase.
- the voltage between points (+) and (-) will be
zero as long as the resistances in the different
arms of the circuit are properly balanced

as solute emerge from column:

change in thermal conductivity  change in
amount of heat removed from resistor  change
in resistor’s temperature and resistance 
change in voltage difference between points (+)
and (-).

-one resistor in contact with mobile

phase leaving column

-another in contact with reference

stream of pure mobile phase
 TCD

advantages:
- truly universal detector
‚ applicable to the detection of any compound in GC
- non-destructive
‚ useful for detecting compounds from preparative-scale columns
‚ useful in combination with other types of GC detectors

disadvantage:
- detect mobile phase impurities
- sensitive to changes in flow-rates
- limit of detection
‚ ~ 10-7 M
‚ much higher then other GC detectors
 2.) Flame Ionization Detector (FID)
- most common type of GC detector
- “universal” detector capable of measuring the presence of almost any organic and many
inorganic compound

Process
- measures the production of ions when
a solute is burned in a flame.
- ions are collected at an electrode to
create a current

advantages:
- universal detector for organics
‚ doesn’t respond to common inorganic compounds
- mobile phase impurities not detected
- carrier gases not detected
- limit of detection: FID is 1000x better than TCD
- linear and dynamic range better than TCD
disadvantage:
- destructive detector
 3.) Nitrogen-Phosphorus Detector (NPD)
- used for detecting nitrogen- or phosphorus containing compounds
- also known as alkali flame ionization detector or thermionic detector

Process Alkali Bead

- same basic principal as FID
- measures production of ions when a solute
is burned in a flame
- ions are collected at an electrode to
create a current
- contains a small amount of alkali metal
vapor in the flame
- enhances the formation of ions from
nitrogen- and phosphorus- containing compounds
 3.) Nitrogen-Phosphorus Detector (NPD)
advantages:
- useful for environmental testing
‚ detection of organophosphate pesticides
- useful for drug analysis
‚ determination of amine-containing or basic drugs
- Like FID, does not detect common mobile phase impurities or carrier gases
- limit of detection: NPD is 500x better than FID in detecting nitrogen- and
phosphorus- containing compounds
- NPD more sensitive to other heterocompounds, such as sulfur-, halogen-,
and arsenic- containing molecules

disadvantage:
- destructive detector
- NPD is less sensitive to organic compounds compared to FID
 4.) Electron Capture Detector (ECD)
- radiation-based detector
- selective for compounds containing electronegative atoms, such as halogens

Process
- based on the capture of electrons by
electronegative atoms in a molecule
- electrons are produced by ionization of the
carrier gas with a radioactive source
‚ 3H or 63Ni
- in absence of solute, steady stream of
these electrons is produced
- electrons go to collector electrode where
they produce a current
- compounds with electronegative atoms
capture electrons, reducing current

advantages:
- useful for environmental testing
‚ detection of chlorinated pesticides or herbicides
‚ detection of polynuclear aromatic carcinogens
‚ detection of organometallic compounds
- selective for halogen- (I, Br, Cl, F), nitro-, and sulfur-containing compounds
- detects polynuclear aromatic compounds, anhydrides and conjugated
carbonyl compounds
• Particularly sensitive to halogens nitriles,
carbonyls, nitro compounds ECD
• 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
• Widely used for the determination of
pesticides, herbicides and PCBs in
environmental samples.
• Non-destructive
QUALITATIVE ANALYSIS OF GC
 QUANTITATIVE ANALYSIS IN GC

1. AREA NORMALIZATION
2. NORMALIZATION WITH RESPONSE FACTOR
3. EXTERNAL STANDARD
4. INTERNAL STANDARD
5. STANDARD ADDITION
AREA NORMALIZATION

31
NORMALIZATION WITH RESPONSE
FACTOR

32
NORMALIZATION WITH RESPONSE FACTOR
34
 EXERCISE
2. Seorang analis diberi tugas untuk menganalisis komposisi sampel asam lemak.
Diperkirakan sampel tersebut terdiri atas asam miristat, asam palmitat, asam stearat, dan asam
oleat. Analis tersebut menganalisis dengan menggunakan kromatografi gas dengan cara normalisasi
respon faktor. Ditimbang standard asam miristat, asam palmitat, asam stearat dan asam oleat
masing-masing sebanyak; 0,1237 g; 0,2344 g; 0,4452 g; dan 0,2271 g lalu dicampur homogen.
Kemudian standard dan sampel diinjeksikan ke alat kromatografi gas dan diperoleh area sbb:
Komponen Area
STANDARDAsam miristat 1236612
Asam palmitat 2077365
Asam stearat 4410998
Asam oleat 2378661
SAMPEL Asam miristat 1203562
Asam palmitat 2213835
Asam stearat 3378927
Asam oleat 2237829

Tentukan:
a. Persen berat (%w/w) masing-masing komponen pada standard
b. Nilai respon faktor masing-masing komponen (RF asam miristat = 1,0000)
c. Komposisi (%w/w) masing-masing komponen dalam sampel
 ANSWER
STANDARD (a) (b)
Berat %W Area %W~area RF
0,1237 12,01 1236612 9,70801E-06 1,0000
0,2344 22,75 2077365 1,09506E-05 1,1280
0,4452 43,21 4410998 9,79518E-06 1,0090
0,2271 22,04 2378661 9,26571E-06 0,9544
1,0304

SAMPEL
©
Area RF A X RF %
Asam miristat 1203562 1,0000 1203562 13,0
Asam palmitat 2213835 1,1280 2497206 27,0
Asam stearat 3378927 1,0090 3409337 36,9
Asam oleat 2237829 0,9544 2135784 23,1
9245889
EXTERNAL STANDARD

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INTERNAL STANDARD

38
39
INTERNAL STANDARD

43
STANDARD ADDITION

44
STANDARD ADDITION

45