the foundations: classical split and splitless injection nicholas h. snow department of chemistry...
TRANSCRIPT
![Page 1: The Foundations: Classical Split and Splitless Injection Nicholas H. Snow Department of Chemistry Seton Hall University South Orange, NJ 07079 snownich@shu.edu](https://reader035.vdocuments.mx/reader035/viewer/2022062515/56649c7f5503460f94934f82/html5/thumbnails/1.jpg)
The Foundations: Classical Split and Splitless Injection
Nicholas H. SnowDepartment of Chemistry
Seton Hall UniversitySouth Orange, NJ 07079
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Split and Splitless
• Split– vaporize and remove most of the sample to
waste
• Splitless– vaporize and transfer most of the sample to the
column; use cold trapping and solvent effects to focus bands
• Both use the same hardware
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Split Inlet
• Use for higher concentration samples
• ppm and above
• hot inlet; vaporize sample
• mix with carrier gas
• use purge valve to “split” the sample– split ratio is critical
• place fraction of sample on column
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SPLIT INJECTION
• High Temperature• High Linear Velocity• Rapid Transfer• Bulk of Sample
Wasted• Split Ratio Important• Liner Geometry
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Classical Split Ratio Determination
• Measure column flow from tm
– Fc = r2L/tm
• Measure purge vent flow using flow meter– Fs
• Split Ratio = Fs / Fc
What are the problems with these measurements?Do we really ever know how much we injected?Does the exact injection volume matter?
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Modern Split Ratio Determination
• EPC systems measure pressures and flows directly
• Column flow is calculated from inlet conditions and column dimensions– add equation here
• Purge flow adjusted to desired value
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Flow Equations
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Advantages of Split Inlets
• Reduced sample size (narrow bands)
• Fast inlet flow rate (narrow bands)
• Dirty samples OK
• Simple to operate (best for isothermal GC)
• Inject “neat” samples
• Excellent interfacing
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Disadvantages of Split Inlets
• Nonlinear splitting– high molecular weights can be lost preferentially
• Thermal degradation – hot metal surfaces can lead to reaction
• Syringe needle discrimination
• Trace analysis limited – ppm detection limits with FID
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Split Injection Techniques
• Filled Needle
• Cold Needle
• Hot Needle
• Solvent Flush
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Split Inlet Discrimination
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Summary - Split Inlet
• Simple
• Hot vaporizing technique– syringe discrimination (best to use autosampler)– liner discrimination
• use glass wool (deactivated)
• shape of liner may be critical
• Best for “neat” or concentrated samples– high ppm or higher
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Splitless Inlet
• Inject sample into hot inlet without “purge”• 95% of sample enters column• Same hardware as split except liner• More variables
– solvent, splitless time, initial column temperature
• Open purge valve after short time• Better sensitivity
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SPLITLESS INJECTION
• High Temperature• Low Liner Velocity• Slow Transfer• Bulk of Sample and
Solvent to Column• Many Factors
Important
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Steps in a Splitless Injection
• Purge valve is off; column is cold• Inject sample
– fast autosampler injection best– slower injections have been proposed
• Flow through inlet is slow; slow transfer to cold column
• After 30-60 sec, open purge valve - cleans inlet• Temperature program column
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BAND BROADENING
• Time
• Space (solvent effect)
• Thermal Focusing
Grob, K., Split and Splitless Injection in Capillary GC, Huthig, 1993, pp. 19-29, 322-36.
Time
Space
Focusing
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Band Focusing Mechanisms
• Splitless injections involve slow transfer to column ---> initial peaks are broad
• Need focusing– cold trap– solvent effects
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Cold Trap
• Initial column temperature cold enough to “freeze” analyte on column
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INITIAL COLUMN TEMPERATURE
40oC 20oC 0oC
-20oC -40oChexane, heptane500 ppb10 min extractionFiber: PDMS 100 mLinermmoCPinj: 1 bar(g)
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Solvent Effects
• Solvent is recondensed in the column
• Long plug of liquid
• Start column 30-50 degrees below normal boiling point of solvent
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Solvent Effects
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Solvent Effects
• Refocus moderate volatility compounds near column head
• Require solvent to wet stationary phase
• Use non-polar solvent with non-polar stationary phase, etc.
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INITIAL COLUMN TMPERATURESOLVENT EFFECT INJECTIONS
0 20Time (min)
0 20Time (min)
40oC 60oC
Solvent: Cyclohexane (bp 81oC), Sample: 10ppm hydrocarbons
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INLET TEMPERATUREREALITY
Set Point 350oC
DistancefromSeptum(mm)
Carrier Gas Temperature (oC)
Klee, M.S., GC Inlets: An Introduction, Hewlett Packard, 1991, p. 42.
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INLET TEMPERATURECHROMATOGRAMS
70000
40000
250oC
100oC
1. octane2. decane3. tridecane4. tetradecane5. pentadecane
HP 5890-5972Pinj = 5.0 psiHP5 30m x 0.25mmx 0.25 mmTransfer: 280oC
1
2
3 4 5
TP: 40oC initial, 1 min, 10oC/min
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INLET PRESSURE
• Linear Gas Velocity IncreasedInjectorColumn
• Analyte Boiling Point Increased
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PRESSURE PULSE
• Increased Pressure During Injection Only
Time (min)
Pressure(kPa)
50
150
0.75
Purge “ON” Time
20
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PRESSURE PULSE
No Pulse
10 psi pulse
12
3 4 5 1. octane2. decane3. tridecane4. tetradecane5. pentadecane
HP 5890-5972Pinj = 5.0 psiHP5 30m x 0.25mmx 0.25 mmTransfer: 280oC
Pressure increased to 15 psig during splitless period
TP: 80oC initial, 1 min, 10oC/min
20000
40000
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OPTIMIZATIONSPLITLESS INJECTION
• Can Be Difficult
• Minimize Transport Time (high linear velocity)
• Maximize Thermal Focusing (low initial column temperature)
• Maximize “solvent effect” (low initial column temperature)
• Chemistry remains a factor
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REFERENCES
• Grob, K. Split and Splitless Injection in Capillary GC, 3rd. Edition, A. Huethig, 1993.
• Klee, M.S., GC Inlets: An Introduction, Hewlett Packard, 1991.
• Stafford, S.S., Electronic Pressure Control in Gas Chromatography, Hewlett Packard, 1993.