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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