Split / Splitless Injection for Capillary GC

Speakers

John V Hinshaw Tony Taylor

CHROMacademy GC Dean CHROMacademy Trainer
‘GC Connections’ editor Technical Director,
Crawford Scientific
Moderator

Dave Walsh
Editor In Chief
LCGC Magazine
Aims & Objectives
1. Overview of Injectors for Capillary GC
2. Injector components
3. Split / Splitless Injection Overview
4. Gas flows in Split and Splitless Mode
5. Critical operating parameters in Split
and Splitless mode
6. Optimising injector settings for
maximum sensitivity and repeatability
7. Inlet liners – the critical facts
8. Troubleshooting Inlet Hardware
9. Investigating Irreproducibility and
Poor Peak Shape
Overview of Injectors for Capillary GC
1. Injectors and Inlets are used to introduce the sample to
the GC column
2. Different classes of Injectors and Inlets available:
a. Vaporising Injector (including Split / Splitless)
b. Cool-on-Column Injector (Thermally Labile or
Accurate Low Level Quant)
c. Large Volume / Programmed Thermal Vaporising
Injector
d. Headspace Inlet
e. Purge and Trap Inlet
f. Thermal Desorption Inlet
g. Pyrolysis Inlet
Characteristics of GC Injectors
1. Low / No Contribution to
Band Broadening
2. Introduces representative &
homogenous sample
3. No discrimination based on
differences in analyte b.pt.,
polarity, concentration
4. Avoids thermal / catalytic
degradation
5. Good accuracy & precision
with a wide range of analyte
concentrations
Injector Anatomy
01_overview.flv
Split Injection Mechanisms I
1. Sample syringe pierces septum
which seals around needle
2. Sample rapidly introduced into
heated inlet
3. Liquid sample volatilises and
the gaseous ‘plasma’ is
contained within a quartz glass
liner
Split Injection Mechanisms II
4. The sample gas is swept by the
carrier gas through the liner
and EITHER into the GC
Column OR between the liner
and inlet body and down the
Split Line
5. % of sample reaching the
column depends upon the
relative flow rates in the
column and split flow line
02_Split_Inj.flv
Setting the Split Ratio I
1. Split ratio is the ratio of gas
flows through the column and
split line
2. Represents the volume
fraction of sample entering
the column
3. Split Ratios from 1:1 to 500:1
are common
4. Higher split – smaller amount
of sample on column
Setting the Split Ratio II
5. Avoids column overload –
fronting peaks and poor area
reproducibility
6. Column capacity depends upon
film thickness, column i.d.,
polarity and retention
7. HIGHER split ratios give
SHARPER (more EFFICIENT)
PEAKS
03_Split_Ratio.flv
Effect of Split Flow on Peak Shape
1. As split flow increases Liner Flow
increases
2. Liner flow is a combination of the
column flow and the split flow
3. Gaseous sample is transferred
more rapidly onto the column
4. Net result is a decrease is analyte
band width (peak width) at the
column head
5. The analyte band will disperse
during elution but initial
bandwidth has impact on peak
effciency
05_peakShape.flv
Split Injection Discrimination
Normalised response of n-alkanes in Hexane
06_discrimination.flv
Split Injection Set-Up Summary
1. Used as the Default Vaporising Injector
2. Primarily used for non-trace analysis of volatile samples
3. Need to consider gas flows (particularly split flow)
carefully / Don’t forget septum purge flow!
4. Increasing split flow:
a. Improves peak shape
b. Lowers column loading
c. Lowers analytical sensitivity
d. Decreases analyte inlet residence time – therefore
reduces the opportunity for thermal degradation
5. Need to consider Discrimination effects
Split Injection Default / Development
Conditions
Temperature: 250oC
Mode: Split
Septum Purge flow: 1-3 ml/min (instrument dependant)
Split Flow: 100ml/min
Column Flow: 0.5 – 2 ml/min (note: depends upon column)
Injection Volume: 1ml (check for backflash)
Liner: Straight through (deactivated and packed if
necessary)
Injection Solvent: Match to column chemistry
Column Temp.: 50 - 100oC (note: analyte dependant)
Split Injection Advantages &
Disadvantages
Advantages Disadvantages
1. Simple to Use 1. Not suitable for ultra-trace
2. Rugged Design analysis
3. Narrow analyte band 2. Suffers from
on column Discrimination
4. Protects column from 3. Liner geometry dictates
involatile sample injector settings
components 4. Analytes susceptible to
5. Easy to Automate thermal degradation
Splitless Injection Mechanism I
1. Same principle as Split
Injection
2. DIFFERENCES INCLUDE
3. Initial injector state is
SPLITLESS i.e. The split line flow
is turned off
4. All sample reaches the column
5. Sample vapours trapped onto
head of column (solvent and
thermal effects)
Splitless Injection Mechanism II
6. Column temperature
programmed to initiate elution
7. At some point after analyte
transfer to the column the
split line is turned on to empty
the injector
8. Primarily used for trace and
ultra-trace analysis
07_Splitless.flv
Splitless Injection Gas Flows I
1. Flow through the liner =
Column Flow during Splitless
phase
2. Analyte can take MINUTES to
transfer to the column
3. If no action is taken,
chromatographic peaks will
be unacceptably wide
Splitless Injection Gas Flows II
4. The answer is to ‘FOCUS’
the analytes onto the
head of the column using
Thermal and Solvent
focussing effects
5. The SPLITLESS (Split-On or
Purge) time needs to be
carefully considered
08_Liner_Flow.flv
Splitless Analyte Thermal Focussing

Rule of thumb:
Initial Oven Temp
10oC < Solvent B.Pt.
09_thermal_focussing.flv
Splitless Analyte Solvent Focussing
N-alkanes in CS2
10_solvent_focussing.flv
Splitless Analyte Solvent Focussing II
N-alkanes in CS2 with Wax Column

Rule of thumb: Match solvent and column polarity

11_solvent_focus_2.flv
Splitless Injection - Optimising Purge
Time
Use the peak area of an early eluting
peak to determine analyte transfer time
Splitless Injection Default / Development
Conditions
Temperature: 250oC
Mode: Splitless
Septum Purge flow: 1-3 ml/min (instrument dependant)
Purge Time: 30 seconds (NOTE: optimise empirically)
Split Flow: 100ml/min
Column Flow: 0.5 – 2 ml/min (note: depends upon column)
Injection Volume: 1ml (check for backflash)
Liner: Straight through (splitless liner)
Injection Solvent: Match to column chemistry
Column Temp.: <10oC below solvent B.Pt.
Split Injection Advantages &
Disadvantages
Advantages Disadvantages
1. Simple to Use 1. Need to carefully optimise
2. Rugged Design conditions
3. Excellent for trace 2. Risk of backflash
analysis 3. Analytes susceptible to
4. Less Risk of Analyte thermal degradation
Discrimination than
Split Mode
5. Easy to Automate
Optimising Injection Volume

1. Solvent vapour volume should not

exceed liner volume
2. Blank solvent injection following
sample will give a ‘mini-chromatogram’
12_optimising_injection.flv
Calculating Optimum Injection Volume
1. Vapour expansion volume is
dependant upon:
a. Solvent type
b. Injection Port Temp.
c. Inlet Pressure

2. Backflash dependant upon:

a. Liner Type
b. Vapour expansion
volume
c. Injection Volume
13_backFlash_calc.flv
Liners for Split / Splitless Injection

Straight Top Middle Bottom Liner i.d.

Through Features Features Features
Troubleshooting – Temperature / Activity
Thermal Degradation
If in doubt use 250oC as an inlet starting point

Peak Tailing
1. Consider Volumetric tailing
(due to unswept dead volumes)
2. Chemically de-activate the
Liner / inlet / column
Troubleshooting – Septa
Septum Bleed Septa Considerations
1. Temperature Limit
2. Size
3. Material
4. Sandwich
5. PTFE Faced
6. Pre-Drilled
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