Basics in Gas Chromatography

GC-Training

Basics in Gas Chromatography

Chromatography is a
technique for separating a
mixture of substances,
using different moving
speeds of the substances
(Translation from Brockhaus 2005)

GC-System

Injector
Detector
Data Processing
Pneumatic
Controller

Column

Gas Supply
Column Oven

Chromatogram

Pneumatic Control

Pressure Control

Pressure
Control
Gas Supply

Pneumatic
Controller

Flow Control

Velocity Control

Pneumatic Control

Pneumatic Control
Column = Tube = Restrictor
Pressure
Control
Gas Supply

Pneumatic
Controller

Column

Flow rate and Linear Velocity:

1. Flow rate [cm3/min],
Typically related to Column Outlet under
SATP (Standard Ambient Temperature and Pressure)

Flow

[cm3/min]

1,013 bar, 25C

2. Average Linear Velocity [cm/sec]

= L /tu
L

= length of column [cm]

tu
= retention time for an unretained peak
[sec]

[cm/sec]

Flow rate and Linear Velocity:

Linear Velocity
can be set as a control
parameter for GC-2010
Series, GC-2014 and
GC2025

Headline for slide (Text only)

Injector

Pneumatic
Controller

Packed Column Injector

and Widebore
Split-/Splitless Injector

Gas Supply

Programmed Temperature
Vaporisation and On Column
Injector (PTV/OCI)

Split-/Splitless Injector
The total flow is the
summery of purge,
split and column flow

Split Injection System

is to inject a sample
with high concentration

Only a defined part

of the sample go
through the column.
the rest go through
the Split out

The purge flow is to

purge the septum

Split-/Splitless Injector

Splitless Mode

10

Split-/Splitless Injector
Two Types of Liner
25mm

25mm

5,5mm

Very Important !
The glaswool must
be
In the correct
possition

Split Liner

11

Splitless Liner
(WBI)

Injection Efficiency
Bad sample transfer on the
column can be due to an
overloaded liner. Important is
the volume of the evaporated
sample not liquid.
Typical liner volume might
vary from 1.0 to 0.1ml
SPL-2010 Plus liner 0.86ml

12

Wide Bore Injector

n a direct injection system,

a wide-bore column is
used. Nearly the entire
amount of sample injected
s inrtoduced on the
column. This usually results
n better sensitivity than
narrow-bore columns with
split injections. However,
peak shapes are broad,
which decreases resolution
and can lead to a higher
S/N ratio. The direct
njection system uses a
WBI (wide-bore injection)
njection port. When WBI
s specified, DIRECT
njection mode is
automatically used and split
mode is not available on
the [INJ] key main screen.

13

Direct Injection System

OCI/PTV
(On Column/Programmable Temperature
Injector)

In the case of OCI

you have to use the
adapter for OCI

14

To install the column you

have to fix the graphite
ferrule with the corect
lenght. Then insert the
column until it reaches the
top end of the adapter for
OCI

A short coffee break

15

GC-System

Injector

Pneumatic
Controller

GC- Column
Column

Gas Supply
Column Oven

16

Gas Chromatography
Separation
Interaction of Forces

Compound

Mobile Phase

17

Stationary Phase

GC Columns:

Packed Column

Capillary Column

Stainless Steel
Glass
Teflon

Fused Silica
Stainless Steel
Glass

Typical size:
1/8 or 1/4 inch o.d.
1 to 3 m lengh

Typical size:
0.25 or or 0.32 mm i.d.
10 to 100 m lengh (30m typ.)
0.5 to 3 ml/min flowrate

10 to 60 ml/min flowrate
0.1 mm i.d. for Fast GC
0.53 mm i.D. for Wide Bore
18

Packed vs Capillary
Analysis of light oil

Capillary

Packed

19

Influence of temperature on
separation efficiency
Isothermal Analysis

20

temperature

temperature

Temperature Programming
Analysis

Classification of Capillary
Colunms
Mobile Phase
- Gas
- Gas

Stationary Phase
- Liquid
(GLC)
- Solid
(GSC)

Application Fields:
(Examples)

21

Environment
Chemistry
Petrochem
Food
Pharmacy
Drugs
..

Capillary columns
Polymid
stat. Phase

Capillary column types

Fused Silica

WCOT =
(GLC)

Wall coated open tubular columns

PLOT = Porous layer open tubular columns

(GSC)
SCOT = support coated open tubular columns
(GLC)
(Special PLOT columns, stationaly phase is
additionally coated with a special
22

Classification of WCOT
Capillary Colunms

B
ore,I.D
m
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ethod

23

Capillary Column
Gas - Liquid - Chromatography
(GLC)
Carrie
r Gas

Different compounds should be separated on

the GLC Capillary Column

24

Phase Distribution

25

Capillary Column
Gas - Liquid - Chromatography
(GLC)
Carrie
r Gas

Separation Mechanism:
1.Vapor Pressure
2.Polarity

26

Theory for GLC

p0i

27

Vapor Pressure
Polarity

Optimizing Capillary Column

Parameters
-Stat. Phase
-Length
-Inner Diameter (I.D.)
-Film I.D.

Selectivity
Resolution
Analysis Time
Sampleamount for
28

Injection

Stationary Phase
Non Polar

Medium Polar

High Polar
29

Stationary Phase defines

Selectivity
OV-1

Increasing Polarity

Grob-Mix Compounds
SE-54

OV-210

OV-1701

CW 20M

30

1
2
3
4
5
6

n-C10
n-C11
N-Octanol
2,6-Dimethyleaniline
2,6-Dimethylephenol
Dicyclohexyleamine

7,8,9 Methyle-Esters from

C10,C11,C12

Resolution RS and Column

N+1
N

Wb(N)
Inject
tmobil

31

tN

Optimizing Resolution by Colunm Parameters:

Column Length
I.D. of the Column
Thickness of inner Film

Resolution vs. Column Length

Resolution Length
5m

Resolution

50 m

25 m

Column Length [m]

2.5 m

12 m

32

Increasing the Column Length is

less efficient due to Peak
Resolution

Theoretical Plates of a Column

Theor. Plates:

tmobile
tR
tN
Wb

N = 16 x (tN /wb)2

= 1,00 min
= 4.803 min
= 3.803 min
= 0.049 min

Describing Separation Efficiency

The number of Theoretical Plates

is always related to a reference
compound, e.g. C12

tR

Wb
Example:
33

N = 96.000

HETP
HETP = Height Equivalent of a Theoretical Plate

HETP = L/N
L = Length of a Column
HETP is a suitable Parameter describing the efficiency of separation

Decreasing value for HETP = Increasing separation efficiency

34

Linear Velocity vs. HETP

Van Deemter Curve

HETP = A + B/u + Cu
A: Eddy Diffusion
(konstant, only Packed Column)

B: Axial Diffusion of Molecules

C: Molecules transferring Phases

35

Decreasing I.D. = Decreasing HETP

HETP and Column I.D.

With smaller
Column I.D. the
influence of higher
flow rates is much
less, due to faster
transfer of sample
molecules
between the
Stationary- and
Gasphase

Most
Effective
36

Example Using different

Columns

Conclusuion:

C30
C20

C24

C28

C32
C36

Red:

0.53mm I.D. , 0.25m Film , 15 m

Green: 0.22mm I.D. , 0.25m Film , 25m

Base With C40

37

Much more Separation

Efficiency with 0,22 mm
I.D.

Film Thickness of Stationary

Phase
The relevance of the Film Thickness is
depending on the Column I.D.

Phase Ratio dc/4df

Volume ratio gas volume to liquid volume
Polymid
dc

stat. Phase df

38

Fused Silica

Phase Ratio

Tendency:
is high
Good separation for high
boiling Componds
is low
Good separation for low
boiling Componds

Film Thickness of Stationary

Phase
Phase Ratios for different df , dc

df (m)
0,1

0,2
500

0,2

250

313

400

663

0,33

152

190

250

400

0,5

100

125

160

265

63

80

133

40

66

1
2
39

dc (mm)
0,25
625

0,32
800

0,53
1325

Film Thickness of Stationary

Phase
For rough Orientation

40

HETP and Carrier Gas

Conclusion:
Nitrogen
Helium
Hydrogen

Approximately no
difference for minimum
HETP comparing the
Gases
Major differences due
to higher flowrates

41

Dodecanoic acid methyl ether

dicyclohexylamine

Unecanoic acid methyl ether

Decanoic acid methyl ether

n-octanol
n-undecane
2,6 dimethylphenol

n-decane

Example Normal GC vs. Fast

GC
DB-5 MS: 30m, 0.25 mm,
0.25 m
140C 1 min, 10C/min to
280 C,2 min
FWHM = 3 s

He 40 cm/s, split 20:1

15 min
RTX-5 : 10m, 0.1 mm, 0.4
m
FWHM = 0.48s

42

1,75 min

140C, 1 min
60C/min to 280 C, 2min
H2 120 cm/s, diluted 10:1,
split 200:1

Sample Amount and Column

I.D.

43

Sample Amount and Column

I.D.

44

Finish
45