Gas Chromatography Basic

Prayoga
Basic principle

• Gas chromatography (GC) is an analytical technique applicable to gas, liquid, and solid samples (components
that are vaporized by heat). If a mixture of compounds is analyzed using GC system, each compound can be
separated and quantified.
• When a mixed solution sample is injected into the GC system, the compounds contained in the sample,
including the solvent components, are heated and vaporized within the sample injection unit.
• With GC system, the mobile phase, referred to as the carrier gas, always flows in sequence from the sample
injection unit to the column, and then to the detector. The target components that were vaporized in the
sample injection unit are transported by the carrier gas to the column. Once in the column, the mixture of
compounds is separated into the various components, and the amount of each compound is then measured
by the detector.
• The detector converts the amount of each compound into an electrical signal, and sends these signals to a
data processing unit. The data obtained enables determination of the compounds contained in the sample,
and in what amounts.
Gas Chromatography Separation
Instrumentation
1. Carrier Gas
2. Injection Port
3. Colomn
4. Detector
5. Data Processor
1. Carrier Gas
• Carrier gas is an inert gas used to carry samples. Helium (He), nitrogen (N 2), hydrogen (H2), and argon (Ar) are
often used. Helium and nitrogen are most commonly used and the use of helium is desirable when using a
capillary column.
• As carrier gas constantly flows into the detector, high-purity gas of at least 99.995 % needs to be used. (The
use of high-purity gas reduces baseline noise.)

Carrier Gas Pros Cons

▪ High diffusitivity and linear velocities ▪ Flammable
▪ Good separation efficiencies ▪ Not completely inert (reacts with
Hydrogen ▪ Short analysis and run time some compounds at high
temperature)
▪ Inert ▪ Expensive
Helium ▪ Non flammable ▪ Not easily available
▪ Gives high resolution
▪ Cheap ▪ Not suited use in temperature
▪ Easily available programmed GC analysis
Nitrogen ▪ Lower or poor separation
▪ Long analysis and run time
Relationships between Column Efficiency (HETP), Carrier Gas Types, and Linear Velocity (Conceptual Diagram).

The column efficiency varies in accordance with the combination of the type of carrier gas used and the analysis
conditions (linear velocity). When using a carrier gas, a suitable linear velocity needs to be specified based on the
relationships between the column efficiency (HETP), carrier gas type, and linear velocity shown in the figure above.
In conventional analysis using a capillary column, around 30 cm/sec of linear velocity is used because helium is often
used as the carrier gas.
2. Injection Port - Sample Injection Volume

• The guidelines for sample injection volumes are as follows. If the injection volume is too large, the peak
shape will become deformed, or the injection port will become dirty, leading to problems.

• Liquid samples: Approx. 1 to 2 µL Gas samples: Approx. 0.2 to 1 mL

• Liquid samples become a gas at the stage of injection into the column. Liquid 1 µL → (Vaporization) → Gas,
Volume: Several hundred to 1000 µL
→ In capillary analysis, it is important to determine how to inject the sample into the column efficiently.
Vaporization Volume of Liquid Samples
Vaporization Volumes of Various Solvents at an Injection Unit Temperature of 250 °C and a Pressure of 140 kPa

Injection Volume (µL)

Solvent
1 2

Isooctane 110 220

N-hexane 140 280

Toluene 170 340

Ethyl acetate 185 370

Acetone 245 490

Dichloromethane 285 570

Carbon disulfide 300 600

Acetonitrile 350 700

Methanol 450 900

Water 1010 2020

2. Injection Port - Sample Injection Methods

• There are a variety of sample injection methods available for capillary analysis.
• Hot Injection
- Split: Most of the sample is eliminated as only a portion is injected into the column.
- Splitless: Not split, but only for 1 to 2 minutes after injection
- Total volume injection (Direct injection): There is no splitting mechanism.
• Cold Injection
- Cold on-column injection (OCI)
- Programmed temperature vaporization (PTV)
Reference Information
Guidelines for Applicable Samples, Injection Volumes, and Columns for Each Injection Method
This table shows the standard sample injection volumes and columns for each injection method.

Hot Injection Cold Injection

Injection Cold On- Programmed
Method Split Splitless Total Volume Column Temperature
Injection Vaporization

Liquid Sample Yes Yes Yes Yes Yes

Gas Sample Yes － *1 Yes － －

Liquid Liquid
sample: 2 µL sample: 2 µL
Injection
max. 2 µL max. max. 0.5 to 2 µL 1 to 8 µL
Volume
Gas sample: 1 Gas sample:
mL max. 0.5 mL max.

Wide bore
Wide bore
columns with
No limits on I.D. 0.25 mm columns with No limits on
Column an I.D.
I.D. or length min. an I.D. of 0.53 I.D. or length
between 0.45
mm × 30 m
and 0.53 mm
Syringes
When injecting samples into a GC unit, a microsyringe is used for liquid samples
whereas a gas-tight syringe is used for gas samples.
 2. Injection Port - Split Injection Methods

The split injection method is the most widely used injection method for capillary analysis. The optimal column flowrate
(average linear velocity) for separation can be set, enabling high-separation analysis. Analysis can be performed at a wide
range of concentrations, from medium to high, and it is suitable for relatively high-concentration samples.

Some of the carrier gas flows into the septum purge line to remove the components emerging from the bottom of the
septum. The remainder flows into the insert within the sample injection unit. A portion branches off to the column, while
the remainder branches off to the split line (split). With this injection method, most of the sample is eliminated. Only a
portion is injected into the column. For this reason, it is not suitable for trace analysis.

•Notes If the split ratio is small, the peak may

inadvertently broaden at the injection port, reducing the
separation
•Only a portion of the injected sample is injected into the
column, so the sample vaporized within the insert must
be uniform.
→ Be sure to place silica wool within the glass insert.
Depending on the sample, change the amount and
positioning of the wool, or the filler within the insert.
 2. Injection Port - Splitless Injection Methods
This method is used for low-concentration samples that require higher sensitivity than what the split method provides.
In the context of capillary analysis, this is a relatively limited analysis method in terms of the applicable components, so it
is mainly used for trace analysis (several tens of ppm or less).

The time from when the sample is injected until the split line is opened is called the sampling time (splitless time).
Samples that are not injected within this time are eliminated. The volume of sample injected into the column is
determined by the formula: Column flowrate × Time. This is unrelated to the split ratio. Peak broadening can be avoided
by keeping the column temperature lower than the boiling point of the sample during the sampling time.

•Notes A septum purge line is required in

order to reduce the impact of sample
retention and compounds originating from
the septum.
•Programmed temperature analysis is
essential.
•The method is not suitable for gas samples,
low boiling point solvent samples, and
components eluted in the vicinity of solvents.
•The method is difficult to apply to
components that elute faster than the
solvent.
 3. GC Colomn

Two types of columns are used in gas chromatography: packed columns and capillary columns.
Currently the prevailing column type, capillary
Short, thick columns made of glass or
columns produce sharp peak shapes, achieve
stainless steel tubes, packed columns
excellent separation performance, and are suited to
have been used since the early
high-sensitivity analysis.
stages of gas chromatography.
Viewing a cross-section image of a packed column
Packed columns produce broad peak
reveals a tube filled with a particulate substance
shapes and have low separation
called packing. Packed columns have been used
performance, but can also handle
throughout the long history of gas chromatography,
large sample volumes and are not
and many different packed columns have been
susceptible to contamination. They
created for different analytical applications.
are still used today in official
analytical methods and for gas
In contrast, typical capillary columns consist of a
analysis.
thin, fused silica glass tube with a thin, internal
Packed Column liquid phase coating. Capillary columns were
developed after packed columns, and though there
are fewer types of capillary columns, their
separation performance is dramatically superior to
packed columns
3. GC Colomn – Packed colomn

Stainless steel or glass tube filled with particulate packing material (an adsorbent material, or a support material
coated or impregnated with a solid phase).

•Internal Diameter: 2 to 4 mm
•Length: 0.5 to 5 m (most commonly 2 m)
•Packing: Support material with 0.5 to 25 %
liquid phase (partition material) or no liquid
phase (adsorbent material)
•Liquid Phase: Multiple types available
 3. GC Colomn – Capillary colomn

A typical capillary column is a thin, fused silica glass tube, lined with a liquid phase or adsorbent material or
having a chemical bonding layer. Thin metal tubes are also sometimes used as capillary columns.

PLOT column
(contains immobilized porouspolymer/alumina, etc.)

WCOT or chemical bonding column (lined with liquid phase or a

chemical bonding layer)
•Internal Diameter: 0.1, 0.25, 0.32, 0.53 mm
•Length: 5 to 100 m (most commonly 30 m)
•Material: Fused silica glass
•Liquid Phase: Good separation but less variety than packed
columns
3. GC Colomn – Colomn Type and Effect on Separation

Packed columns produce broad peaks and capillary columns produce sharp peaks. In addition, capillary
columns produce taller peaks, which allows the detection of lower concentrations (high detection sensitivity).
This is the advantage of capillary columns.
Sharper peaks provide better separation but also shorter analysis times.
General Guide to Selecting Polarity

• Selecting columns with polar properties that are close to the polarity of the target compounds
－ Analysis of non-polar compounds → Non-polar column
－ Analysis of polar compounds → Strongly polar column

• Selection by analytical objective

－ Large difference in boiling point between analytical target compounds → Non-polar column
－ Isomers or other compounds with little difference in boiling points → Strongly polar column

Guide to Selection of Internal Diameter, Length, and Coating Thickness

• Selection based on required separation

－ High-resolution separation required → Internal diameter: Thin, Length: Long
－ Adequate separation with shorter analysis time → Internal diameter: Thick, Length: Short, Coating
thickness: Thin

• Selection by analytical objective

－ Analysis of low boiling point compounds → Length: Long, Coating thickness: Thick
－ Analysis of high boiling point compounds → Length: Short, Coating thickness: Thin
4. Detector

The detectors that can be used with Shimadzu gas chromatographs are shown below. They are broadly
divided into general-purpose detectors and selective, high-sensitivity detectors. General-purpose detectors
can analyze a wide range of compounds, of which the flame ionization detector (FID) is the most common
because it can analyze almost all organic compounds. In contrast, selective, high-sensitivity detectors are only
capable of detecting specific types of compounds selectively and with high sensitivity.
 Detector Detectable Compound Detection Limit ＊
General-Purpose Detectors
Flame ionization detector (FID) Organic compounds (other than formaldehyde 0.1 ppm (0.1 ng)
and formic acid)

Thermal conductivity detector (TCD) All compounds other than the carrier gas 10 ppm (10 ng)

Barrier discharge ionization detector (BID) All compounds other than He and Ne 0.05 ppm (0.05 ng)

Selective, High-Sensitivity Detectors

Electron capture detector (ECD) Organic halogen compounds 0.1 ppb (0.1 pg)
Organic metal compounds

Flame thermionic detector (FTD) Organic nitrogen compounds 1 ppb (1 pg)

Inorganic and organic phosphorus compounds 0.1 ppb (0.1 pg)

Flame photometric detector (FPD) Inorganic and organic sulfur compounds 10 ppb (10 pg)
Inorganic and organic phosphorus compounds
Organic tin compounds

Sulfur chemiluminescence detector (SCD) Inorganic and organic sulfur compounds 1ppb （ 0.1pg ）
4. Detector – Detector Gas and Makeup Gas
Each detector requires gas, called the detector gas, based on its principle of detection. For example, the flame
ionization detector (FID) uses a hydrogen flame so it requires hydrogen and air.

Analysis using a capillary column can also require a makeup gas added just before the detector to act as an
auxiliary gas and ensure the detector receives a rapid supply of compounds. Makeup gas reduces the effects
of increasing and decreasing column flowrates on detector sensitivity by increasing the sample transfer speed
inside the detector and preventing peak broadening.
Detector Detector Gas Makeup Gas (Capillary)

FID H2 and Air He or N2

TCD Unnecessary He or Ar or N2 or H2 ,etc.

BID He None

ECD Mainly N2 (The combination of gases varies by equipment model.)

FTD H2 and Air He

FPD H2 and Air None (required in some models)

SCD H2 and O2 N2
 4. Detector – Flame Ionization Detector (FID)
The FID is the most common detector used in Schematic Diagram of the FID
gas chromatography. The FID is sensitive to,
and capable of detecting, compounds that The FID creates a hydrogen flame by burning air and hydrogen
contain carbon atoms (C), which accounts for supplied from below. The carbon in a sample carried into the
almost all organic compounds. However, the detector on carrier gas is oxidized by the hydrogen flame, which
FID is not sensitive to carbon atoms with a causes an ionization reaction. The ions formed are attracted by
double bond to oxygen, such as in carbonyl a collector electrode to an electrostatic field, where the
groups and carboxyl groups (CO, CO2, HCHO, components are detected.
HCOOH, CS2, CCl4, etc.).

< Main Applications >

•Organic compound analysis
Flame Photometric Detector (FPD) FPD is a highly selective and sensitive detector, especially for
phosphorus (P), sulfur (S), and tin (Sn) compounds. It detects light unique to P, S and Sn in the
hydrogen fame through interference flter. FPD is so stable and sensitive that it is easy to use
alongside selective detectors. It has been used in food analysis, — to detect phosphorus pesticides,
sulfur odors and food favors — and in environmental analysis to detect organic tin compounds in
sea products.
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