MS Basics and Hardware Configuration
MS Basics and Hardware Configuration
In this section you will learn: How the MS Compares to the Other GC Detectors Functional Components of the MS Fundamentals of Mass Spectrometry How to Configure Your GC-MS System
GC Detectors
Thermal Conductivity Filament pair heats when sample dilutes carrier gas
PMT
2 H
REF
Flame Photometric Optical filter selects wavelength specific to P or S compounds
Air
Flame Ionization Burning produces charged particles which collector converts into a current
NP Thermionic N or P compounds increase current in plasma from vaporized metal salt
Electron Capture Loss of slow electrons by sample absorption decreases cell current
Ion Source Analyzer EM
Mass Selective Detector Ionized sample measured by mass analyzer
Comparison of GC Detectors
TCD FID ECD NPD(N) NPD(P) FPD(S) MSD (SIM) 10-15 fg 10-12 pg (SCAN) 10-9 ng 10-6 ug 10-3 mg
1 ng in 1 uL Liquid (sg = 1) is 1 ppm Concentration Mass Selective Detector is both: Specific and Universal
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Functional Components of the MS
EXHAUST
MECHANICAL PUMP
HI VAC PUMP
MASS SPECTROMETER ION SOURCE MASS FILTER
GC
INTERFACE
DETECTOR
CONTROLLER (ChemStation)
Interfacing GC and MS
GC MSD
10-5 Torr <2 mL/min
760 Torr 0.5 - 15 mL/min
INTERFACE
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Interface Overview
Column Narrow Bore
ID (mm) 0.1 0.2 0.25 0.32 0.53
Typical Flow (mL/min) 0.1 1.0
Interface Capillary Direct
Wide Bore Mega Bore
13 3 15
Splitters Jet Separator Splitters Jet Separator
Vacuum Pumps
Gas ballast valve Discharge port
Optional trap Oil refill port Inlet port Mechanical Pump 10-1 - 10-2 torr
Anti suck-back valve Oil level sight glass
Oil level
Oil reservoir Stator Gravity drain plug Rotor High Vacuum Pump Vents 10-5 - 10-6 torr
Inlet
. Outlet . . . . (to Mechanical Pump) . . . .. .. . . . . . ..... ... .. ..... ..... .... .... . . . .. ...... .. ...... . .
Stack Heater
Baffles (prevent oil loss) 8
Turbo Pump
Axial-Flow Turbine up to 60,000 RPM Rotating Blades Fixed Blades
Blades (airfoils) are angled to deflect gas molecules downward towards the next set of blades and finally to the pump outlet
MOTOR
To Foreline Pump
Lubricating Wick
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MOTOR
Analyser parts
Electron Multiplier Filament Inlet Ion Focus Ion Source Volume Repeller Entrance Lens, AMU gain, offset Mass axis gain, offset offset Mass Filter HED
Filament
Drawout
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Reasons for Vacuum in MS
Provide adequate mean free path Provide collision-free ion trajectories Reduce ion-molecular reactions Reduce background interference Increase filament lifetime Avoid electrical discharge Increase sensitivity
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Electron Ionization (EI)
Ionization: ABC + e Neutral Molecule . ABC + + 2e Excited Molecular Ion
Position of Curve . #ABC+ Depends on IP (ABC)
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70
100 eV Electron Energy
Fragmentation: ABC + . . AB A+ . AB + . AC + etc. + C+ . + BC +C +B
(loss of neutral) (rearrangement)
Resulting Mass Spectrum: + C Signal Abundance + A m/z + AC + AB + . ABC
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Positive Chemical Ionization (PCI)
First forms ions from a reagent gas by bombardment with electrons Reagent gas ions undergo subsequent reactions with sample molecules to form sample ions (Brnsted acid) CI ion formation is much more gentle than electron ionization (EI) therefore less fragmentation Most common reagent gas is methane, produces ions with almost any sample molecule Other reagent gases (isobutane, ammonia) are more selective and even less fragmentation Source pressure ~ 0.2 Torr Detection limits are generally high because of background from the reagent gas (methane) Most often used to determine the molecular weight of a compound
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Negative Chemical Ionization (NCI)
a.k.a. electron capture negative ion chemical ionization First form a cloud of electrons with little excess energy (thermal electrons) Thermal electrons are captured by sample molecules Buffer gas required (removes energy from electrons/ions) Methane is by far the most often used buffer gas Source pressure ~ 0.4 Torr (higher than for PCI mode) Only certain types of molecules are capable of capturing thermal electrons (selectivity) Extremely efficient for some molecules (sensitivity) Detection limits are generally very low due to lack of response from contaminants or matrix Most often used for selective high sensitivity analysis
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How does a Quadrupole Mass Filter Work?
FILTERING HIGH MASS + M NEGATIVE RODS
FILTERING SELECTED MASS M +
POSITIVE RODS
FILTERING LOW MASS M +
POSITIVE RODS
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RF & DC Voltages
(RF & DC Voltages If Mass Is Set To 100AMU)
Optimal +173 Volts (rf & U+) Optimal Optimal
+150 Volts (rf & U-)
Less Than Optimal
Less Than Optimal
+23.26 Volts (U+)
-23.26 Volts (U-)
-150 Volts (rf & U+)
-173 Volts (rf & U+)
Positive Polarity Quadruple
Negative Polarity Quadruple
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X-Ray Lens/Electron Multiplier Detector
X-Ray Lens (0 to 218 V) Signal Out + Incoming Ion
EM Voltage (0 to -3000 V)
Lifetime a Function of Current Detector Gain a Function of EM Voltage
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High Energy Dynode/Electron Multiplier Detector
Positive Ions
+ +-+ + -+ + + --++ + + -+++ +++ + + ++ + ++ + + + + ++++ + ++ ++ + + +++++ + + + + + ---
High Energy Dynode Electrons
Electron Multiplier Quadrupole Iris Detector Focus Lens Signal Out
Lifetime a Function of Current Detector Gain a Function of EM Voltage
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A Typical Mass Spectrum
Dodecane: C12H26 Abundance 100 90 80 70 60 50 40 30 20 10 m/z-> 20 29 55 98 113 128 40 60 80 100 120 141 140 159 160 180 170 85 <--[C H ] + 6 13 M 43 71 + <--[C H ] 5 11 Average spectrum of dodecane from EVALDEMO.D 57 <--[C H ] + (Base peak) 4 9
+ .
(Molecular ion)
Molecular ion (a.k.a. parent ion): loss of one electron Base peak: most abundant ion in spectrum
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Local Control Panel
Diagnostics Vent / Pumpdown Tune Run / Stop
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GC-MS Configuration
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Data Analysis Configuration
Four possible modes of data analysis
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Networking Information
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