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Introduction and Principles of Gas
Chromatography
Jaap de Zeeuw
Restek, Middelburg, The Netherlands
Jaap.dezeeuw@restek.com
Copyrights: Restek Corporation
• Definition and Uses of Gas Chromatography
• GC Components and Types of Columns
• Factors Affecting Chromatographic
Separation
• Basic Terminology and Theory

Which Industries Use Chromatography?
• Chemical/Petrochemical
• Clinical/Forensic
• Consumer Products
• Environmental
• Food
• Pharmaceutical

Why Gas Chromatography?
• Simple
• Cheap (can be automated)
• Short analysis times
• High Accuracy
• Qualitative and Quantitative analysis
• Applicable in % to ppb level

Which components do we see in
General Natural Gas?
• Nitrogen
• Hydrocarbons
• PCBs*
• Tars, Oils, waxes
• Radon
• Olefins
• Sulfur components
• Ethylene Glycol
• Aldehydes
• Phenols & cresols
• Amines
• Organic sulfur
• Organo metallic compounds
• Oxygenates
* Ref: California proposed Public Gas Warning List

Important Separations in Natural Gas analysis
Hydrocarbons Rtx-
Rtx-1 Thin-
Thin-film Nitrogen - methane Rt Q-
Q-BOND
C5 50 m x 0.32 mm CP-Sil 5 CB, 1.2 um
C6 Helium, 160 kPa
40 °C, --> 200 °C, 5 °C/min
C8
C9
C10
C11
40 min
Rtx-
Rtx-1 thick-
thick-film Oxygenates Polar phase (wax)
Sulfur
50 m x 0.32 mm CP-Sil 5 CB, 5 µm 10 m x 0.53 mm CP-Lowox
H 2S
CO2 40,2 °C Natural gas peak 150°C(2 min) -->200°C, 10 °C/min
H2, 65 kPa; TCD
Direct Injection, 50 µl
CH4 + N 2 C2 C3
Methanol 20 ppm
C4
i-C 4
•Methanol well separated
from matrix
•Symmetrical peak for
10 min methanol
9 min

IUPAC Definition of Chromatography
“A physical method of separating sample

components from a mixture by selective
adsorption or partitioning of the analyte between
two phases:
a “mobile phase and a stationary phase”

Chromatography Phases
Mobile Phases
• Liquids (methanol, water…)
• Changing dielectric strength, temperature, pH
• Gases (nitrogen, helium, hydrogen, argon)
Stationary Phases
• Solids (alumina, silica, polymers, carbon…)
• Adsorption chromatography
• Liquids (siloxanes, polyethylene glycols…)

• Partition (distribution) chromatography

stationary phases
• Specialized polymer chemists
Commercial phases
are very dirty.. • Lowest specifications possible
• Innovation, unique phase technologies
High purity /viscosity polymers for low-

bleed and stable stationary phases
GC Components and Types of Columns
• Components of a Gas Chromatograph

• Types of GC Columns
• Types of GC Capillary Columns

Components of a Gas Chromatograph

Gas Purification Equipment
Triple Filter
12
New Filter Used Filter
Triple filter
O2 indicator
New O2 Saturated
Indicator O2 Indicator
Color change
New Filter Used Filter
Triple filter
H2O
indicator
New H2O Saturated

Indicator H2O Indicator
Color change
Components of a Gas Chromatograph

Types of GC columns

Types of GC Columns
Packed Capillary
Length, [meters] 1-6 5 - 150

ID, [millimeters] 0.53-4 0.1 - 0.53
Theoretical plates 5,000 (2m) 120,000 (30m)
Capacity [ng] 10,000 50 (0.25mm ID)
Amount of Liquid phase 1-30 % 0.1-7.0 μm
Price €100 €400 (30m, 0.25 mm ID)

Capillary Column Materials
Fused Silica
• Synthetic, amorphous glass with very low (<1ppm) metallic oxide

impurities
• Protective outer coating of polyimide resin imparts flexibility but coil
diameter is limited
• Excellent inertness and useable up to approximately 380oC(400oC)
Metal Tubing-MXT
• MXT, stainless steel, surface coated, Siltek deactivated

• Can be coiled to small diameter
• Almost as inert as fused silica but useable up to approx. 450ºC
Types of GC Capillary Columns
WCOT (Wall Coated Open Tubular)

• Partition chromatography
• Typical phases: Siloxanes and Polyethylene glycols
• 0.10 to 0.53mm internal diameters
PLOT (Porous Layer Open Tubular)

• Adsorption chromatography
• Gases, light hydrocarbons/solvents analysis
• Adsorbents: molecular sieve, porous polymers, alumina
(<1 um particle diameter)
• 0.25 to 0.53mm internal diameter
Compounds Amenable to Gas Chromatography
• Should be thermally stable
• Should be un-reactive and non-absorptive to

chromatographic system
• Should be volatile at temperatures below 350-400°C

• Presence of polar groups reduces volatility

Sample Transfer
Injection: how the sample is transferred to the column

• As a liquid via syringe
• Non-liquid techniques
• Purge & trap
• Headspace
• Gas sample loop
•NOTE: It is critical to get the sample into the

column in a focused band…
Peak width of eluting component
σ injection + σ column + σ detection = Σ peak
+ + =
+ + =
Sample introduction
Need to realize smallest possible sample band on the capillary column..
Injection Techniques commonly used:
% - 5 ppm levels
• Split Small amount injected
• Splitless Narrow injection band
• Thermal desorption (PTV)

ppm-ppb levels
• Headspace
Large amount injected
• On-Column Must use a focusing mechanism..

Sample Transfer
How to Get a Focused Initial Band
• Analyte Focusing
• Higher boiling components
• Increase retention (stationary phases type, film and
temperature)
• Solvent Focusing
• All components, but must elute later then solvent
itself

Analyte focusing
• If analytes are high boiling, they will be focused by

the retention of the stationary phase
• If analytes have lower boiling points this will show

itself as “smeared” peaks

Analyte focusing: example
“focused” peaks
“Smeared” peaks
Not enough retention for focusing

Solvent-Focusing in splitless injection
• In splitless injection some solvent condensation is

required to create the ”solvent” effect.
• This solvent will trap (= focus) compounds and

makes sure that a narrow band is formed.
• Realization: Oven temperature during injection

must be 20°C below the Bp of the solvent.

Splitless Injection at oven temperature 20°C BELOW
BP of solvent
The “solvent effect” makes

sure all peaks are focused
2 4 6 8 10Copyrights: Restek Corporation

Focusing in Splitless injection
No Focusing: Focusing:
Long Initial Sample Band, Correct solvent peak
broad peaks and narrow peaks

2 4 6 8 10
Split/Splitless injection system
Silicone septum

Split injection Considerations
• 1-3 mL/min into the column

• 10-200 mL/min in the inlet (mostly split vent flow)
Split Ratio:
Column flow rate :1 mL/min
Split vent flow rate : 100 mL/min
Split ratio = Column Flow rate = 1

Split-vent + Column flow rate 100+1
Split ratio ~ 1:100

Impact of Split Ratio
Increasing the split ratio decreases the peak area,

if all other variables are equal.
SPLIT
25:1 Split 50:1 Split
Column
Head Pressure
Total Flow Septum Purge
Split Vent Purge Vent
0 10 0 10
Factors impacting the separation

Non-Column Factors Affecting Separation
• Carrier gas: type & linear velocity

• Temperature
• Injection bandwidth

Gas Carrier and Linear Velocity
Hydrogen : 40-50 cm/sec

Helium : 25-35 cm/sec
Nitrogen : 10-15 cm/sec

Carrier Gas and Linear Velocity
• Isothermal Analysis
• Hydrogen is 2x faster than helium and 4x faster than
nitrogen
• Temperature Programmed Analysis

• Need to optimize temperature program to get SAME
elution temperatures;
• Also here Hydrogen is 2x faster then helium

Hydrogen is of interest
• Fastest analysis
• Availability ( can be generated)
• Need less sample for same signal (maintenance)
Deal with safety issues

• Setting of constant flow (impossible to built up high H2 levels
• Use H2-detection (will cost $, but makes safety officer happy)
• Use metal (MXT) columns (also VERY inert)

Column length
10/15 m < 10 components and Fast analysis

25/30 m 10 - 20 components
50/60 m complex mixtures: > 20 components
Most widely used is 30m
Do we need extreme LONG columns?

Summary:
Effect of Length
• Retention time proportional to length in

isothermal analysis but not proportional in
temperature program analysis
• Gain in resolution is not double, but € are

The BETTER the
Chromatographer….. ... the SHORTER
the column..

Examples where we need LONG columns
• Detailed Hydrocarbon Analysis (>300 components)

• Bio-ethanol (to get isobutane-methanol separation)
• Separation of PCB isomers (209 congeners)
• Separation of Cis and Trans FAME isomers

Column Internal Diameter
0.53 mm
• High flow and loadability
• Direct injection via insert or valve (analyzer)
• TCD detection
• Retention gap for On-column
0.32 mm
• On-column injection;
• Thick films are possible
• Electronic Gas / Pressure Control
0.25 mm
• Ideal for split and splitless injection
• Relatively high plate number
0.18/0.15/0.10 mm
• Short analysis times
• Low bleed / GC x GC

Internal diameter
0.10mm 0.15/0.18mm 0.25mm 0.32mm 0.53 mm
Practically the following dimensions are used :

0.10 <1 %
0.15/0.18 mm 3%
0.25 mm 45 %
0.32 mm 35 %
0.53 mm 10 %

Basic Terminology and Theory
• Resolution (R)
• Theoretical Plates (Neff)
• Height Equivalent to a Theoretical Plate (HETP)
• Phase Ratio (ß)
• Retention (Capacity) Factor (k)
• Retention Time (t)
• Column Selectivity Factor (α)

The Resolution Rs
Quality of Separation
between 2 Peaks
Dimensionless
Parameters:
- Selectivity
- Retention
- Efficiency

Resolution
Resolution depends on:

α : Selectivity
k’ : Retention Factor
Nth : Plate Number

Impact of Nth on resolution
Increase N:
Longer column
Smaller Internal diameter
Impact of Higher N using 2x

smaller diameter, same length

Impact of k on resolution
Increase k:
use thicker film (same column dimensions)
decrease oven temperature (ever 15C, k changes a factor 2)
CH4
Impact of using 2x thicker film,
Same column dimensions and
temp.

Impact of α on resolution
Increase alpha:
use different stationary phase (same column dimensions)
CH4
Impact of using different phase
with higher selectivity

Effective Theoretical Plates (Neff)
Neff = 16 t'
( ) R
2
Wb Dead
Time Wb
t'R
•Adjusted Retention Time = Retention Time – Dead Time
•Wb = Width between tangents of a peak at baseline intercept

Theoretical plates
1 touch = 1 plate
• This nr is the “number” of “touches” of a

component with the stationary phase, while it
moves through the column.

One theoretical plate Carrier gas
Two Theoretical plates

Three Theoretical plates

Theoretical plates
1 touch = 1 plate
• This nr is the “number” of “touches” of a component

with the stationary phase, while it moves through the
column.
• The more “touches”, the more plates, the better the

separation
• Impacted by:
• Column diameter
• Column length

Height Equivalent to a Theoretical Plate (h)
L
h =
N
H depends on Flow and Column ID
Lower h = Improved Separation
Basic equation used in GC: Van Deemter equation

Van Deemter equation
H = A + B/u + Cu
H = height of a theoretical plate
U = average linear gas velocity
A, B, C = different contribution factors to peak broadening

The A - term
Contribution to peak broadening due to different path length
(eddy diffusion)
For capillary columns A = 0

The B - term
Contribution to peak broadening due to multidirectional
diffusion in the Gas phase
Indirect proportional to flow rate

The B - term

The B - term

The C - term
Resistance to mass transfer in the liquid phase
Direct proportional to flow rate

The C - term

The C - term

The C - term

Van Deemter: there is an optimal flow

Van deemter: Gas Carrier and Linear Velocities
Van Deemter Plot

1.0
N2
HETP (mm)
He
0.6
H2
0.2
10 20 30 40 50 60 70
Average Linear Velocity (cm/sec)
Stationary phase Film Thickness
Kapacity factor “K” and Retention

Retention (Capacity) Factor : k
Practical the most effective separation occurs when the k value for
an analyte is minimal 5.
Retention (k) can be influenced
• By film thickness
Retention is LINEAR with film thickness
• By temperature
Every 15°C change in oven temp. the k will
change about a factor 2

Film Thickness and Beta (phase ratio)
0.25 μm 1.0 μm 3.0 μm
0.5 min 2 min 6 min
k is linear with Film thickness

Phase Ratio (ß)
mobile phase volume column radius

β= stationary phase volume = 2x film thickness
Phase ratio is important if you want to change column

internal diameter;
For the most easy method conversions, one should try to
keep the phase ratio the same
Film Thickness Effects : 0.25µm Rtx-1
30m, 0.32mm ID, 0.25µm Rtx-1
70ºC isothermal 1. 1-butanol
2. benzene
1-6
3. 2-pentanone
7 4. C7
8 K C10 = 4.5 5. 1-nitropropane
6. pyridine
9 7. C8
8. C9
9. C10 5.5 min
2 4 6 [min]
Film Thickness Effects: 1.0µm Rtx-1
30m, 0.32mm ID, 1.00µm Rtx-1
70ºC isothermal
1. 1-butanol
1-6 2. benzene
3. 2-pentanone
4. C7
7 K C10 = 18 5. 1-nitropropane
8 6. pyridine
9 7. C8
8. C9
9. C10 19 min.
0 10 20 [min]
Film Thickness Effects : 3.0µm Rtx-1
30m, 0.32mm ID, 3.0µm Rtx-1

70ºC isothermal
1. 1-butanol
2. benzene
1,2,3 6
3. 2-pentanone
5 4. C7
5. 1-nitropropane
6. pyridine
K C10 = 54
4 7. C8
8. C9
7
9. C10 55 min.
8
Peak 9 elutes at 55 min..

0 4 8 12 16 20 24 [min]

Stationary Phase: Column Selectivity (α)
• Interactions with the stationary phase

• pi – pi
• Van der Waals (london)
• Hydrogen bonding
• Depends upon the Chemical
composition of the phase

Column Selectivity
Chemical Composition of Phases
Rtx®-1 Stationary Phase

100% dimethylpolysiloxane
Column Selectivity
Chemical Composition of Phases
Rtx®-5 Stationary Phase

5% diphenyl
95% dimethylpolysiloxane
Column Efficiency, Selectivity,
and Peak Symmetry
Not Efficient, not Selective Not Efficient, but Selective
Efficient, but not Selective Efficient and Selective

Examples of selectivity..

Selectivity via geometry
Separation of Para - en Meta Xylenes
P+M P+M
M O M P M
P O O O
P
O
100 % methyl 50 % phenyl PEG

Squalane Rt-TCEP
Rtx-1 50 % methyl Rtx-Wax
Rtx-17
Non-Polar Polar
Shape selectivity
Using selected cyclodextrins as modifiers
p-xylene
m-xylene
o-xylene

Basic rule in GC stationary phase..
Solubility of sample component in the stationary phase

based upon “likes dissolve likes.”
“ choose a stationary phase that “looks like” the

components you want to separate..”
Hydrocarbons 100% PDMS Rtx-1

Aromatic subst. Phenyl subst. PDMS Rtx-5, 17, 35 RT-Dioxins
Halogenates Arom. Fluorimated-phenyl Rtx-440, Cl-Pesticides, Rtx-200
Solvents Cyano /phenyl Rtx-1301/624
Alcohols PEG Stablewax
Double bonds Cyano propyl Rt 2330, 2460

(GC-MS) Presence of Diethylene Glycol and
Ethylene Glycol in Toothpaste
Column: Stablewax
Dissolves : ‘likes like”

Hydrocarbons on 100% PDMS
n-C4
n-C5
n-C6
n-C7
Column : 100 x 0.25 mm Rtx-1 PONA CB, tuned 5%phenyl PDMS
Oven : 5°C, 10 min -> 50°C, 5°C/min, 54 min, --> 200°C, 1.3 °C/min
Carrier gas : He, 24 cm/s, 39.3 Psi; Injection Split, 1 : 150; Detection : FID;
n-C8
C3
n-C9
0 50 100 n-C10 150

PAHs using an Rxi-17Sil MS (30m x 0.25mm x 0.25μm)
benzo(j)fluoranthene
benzo(b)fluoranthene
benzo(k)fluoranthene
5
4
6
2
1
3
7
8
14,15,16
9
10
12/13
11
17 21/22
20 23
18 24
25
26
19
27

Detection in GC

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Introduction and Principles of Gas

Copyrights: Restek Corporation

Copyrights: Restek Corporation

Copyrights: Restek Corporation

Copyrights: Restek Corporation

* Ref: California proposed Public Gas Warning List

Copyrights: Restek Corporation

“A physical method of separating sample

Copyrights: Restek Corporation

• Liquids (siloxanes, polyethylene glycols…)

Copyrights: Restek Corporation

High purity /viscosity polymers for low-

• Components of a Gas Chromatograph

Copyrights: Restek Corporation

Copyrights: Restek Corporation

Copyrights: Restek Corporation

New H2O Saturated

Copyrights: Restek Corporation

Copyrights: Restek Corporation

Length, [meters] 1-6 5 - 150

Copyrights: Restek Corporation

• Synthetic, amorphous glass with very low (<1ppm) metallic oxide

• MXT, stainless steel, surface coated, Siltek deactivated

WCOT (Wall Coated Open Tubular)

PLOT (Porous Layer Open Tubular)

• Should be thermally stable

• Should be un-reactive and non-absorptive to

• Should be volatile at temperatures below 350-400°C

Copyrights: Restek Corporation

Injection: how the sample is transferred to the column

•NOTE: It is critical to get the sample into the

σ injection + σ column + σ detection = Σ peak

Injection Techniques commonly used:

• Splitless Narrow injection band

• Thermal desorption (PTV)

Copyrights: Restek Corporation

Copyrights: Restek Corporation

• If analytes are high boiling, they will be focused by

• If analytes have lower boiling points this will show

Copyrights: Restek Corporation

Copyrights: Restek Corporation

• In splitless injection some solvent condensation is

• This solvent will trap (= focus) compounds and

• Realization: Oven temperature during injection

Copyrights: Restek Corporation

The “solvent effect” makes

2 4 6 8 10Copyrights: Restek Corporation

Copyrights: Restek Corporation

Copyrights: Restek Corporation

• 1-3 mL/min into the column

Split ratio = Column Flow rate = 1

Split ratio ~ 1:100

Copyrights: Restek Corporation

Increasing the split ratio decreases the peak area,

25:1 Split 50:1 Split

Total Flow Septum Purge

Split Vent Purge Vent

Copyrights: Restek Corporation

• Carrier gas: type & linear velocity

Copyrights: Restek Corporation

Hydrogen : 40-50 cm/sec

Copyrights: Restek Corporation

• Temperature Programmed Analysis