CHEM 4330

Lecture 8

Mass spectrometry-2
Mass analyzers

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Mass analyzers

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 Mass analyzers
Resolution and accuracy of mass analyzers

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 Mass analyzers
Magnetic sector mass spectrometer

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 Mass analyzers
Magnetic sector mass spectrometer
B: magnetic field strength
V: voltage between slits A and B
r: radius of the magnetic sector
e: electronic charge

Ions with different mass, but

constant kinetic energy, are
separated by their trajectories
in a magnetic field.
B is scanned to allow ions of
different mass detected.

Mass spectra can also be obtained

m B 2 r 2e
 by varying V and holding B and r
z 2V constant, OR by varying r and
holding B and V constant. 5
 Detection of Dioxins at ppt to sub-ppt levels

Or by GC-Magnetic sector at SIM

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SIM m/z 319.8960 J Am Soc Mass Spectrom 2010, 21, 1918–1921
 Mass analyzers
Quadrupole mass spectrometer

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 Mass analyzers
Quadrupole mass spectrometer
• Composed of two pairs of parallel metallic rods, one set
is positively charged, the other one at negative potential
• A combination of dc and rf voltage is applied to each set
of rods generating an oscillating electric field in the
region between the rods
• Depending upon the ratio of the rf amplitude and the DC
voltage, ions acquire an oscillation in the electric field
• Ions of the “correct” m/z value undergo a stable
oscillation of constant amplitude and reach the detector
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 Mass analyzers
Quadrupole mass spectrometer
Unit resolution
MS spectrum of methanol as recorded by a quadrupole mass analyzer with EI source

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 Mass analyzers
Quadrupole mass spectrometer

Changing DC voltage linearly as a function of RF voltage,

we obtain a straight operating line that allows us to observe those
ions successively. A line with a higher slope would give us a higher
resolution, so long as it goes through the stability areas. 10
 Mass analyzers
Quadrupole mass spectrometer
Single Mass Transmission mode

Intensity
m3 m4 m2
m2
m2
m1
m2 m2
m/z

Mass scanning mode

m3 m4 m3
Intensity m2
m1 m4
m2
m1

m/z
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 Mass analyzers
Quadrupole mass spectrometer
Selected ion monitoring mode (SIM)
• At a given amplitude of dc and rf voltages, only the
ions of a given m/z ratio will resonate, have a stable
trajectory to pass the quadrupole, reach the detector,
and be detected. Other ions will be de-stabilized and
hit the rod.
• More time can be spent on monitoring each m/z
• High duty cycle, high sensitivity for quantitative
analysis

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 Mass analyzers
Quadrupole mass spectrometer
Selected ion monitoring mode (SIM)

Isotope-dilution MS:
Standard and istopic-labelled IS
have the same retention time,
they are detected separately by
virtue of their different masses.

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 Mass analyzers
Quadrupole mass spectrometer
Scan mode
• The amplitude of the dc and rf voltages are ramped
to obtain the mass spectrum of the specified mass
range (analogous to an optical variable-band filter
photometer).
• Sensitivity is a function of the scanned mass range,
scan speed and resolution

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 Mass analyzers
Quadrupole mass spectrometer
Scan mode

m/z 200-700

m/z 288

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 Mass analyzers
Quadrupole mass spectrometer

Scan Extracted ion chromatogram

(EIC) from MS analysis with
Scan mode

SIM
Enhanced sensitivity &
Selectivity with SIM

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 Mass analyzers
Quadrupole mass spectrometer
GC and LC coupled with quadrupole mass analyzer

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GC-MS with EI source and quadrupole MS LC-MS with ESI source and quadrupole MS
Mass analyzers

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 Mass analyzers
Time-of-flight mass spectrometer
• Ions are accelerated with the same potential
• Ion separation in the flight tube according to
m/z ratio
• The lighter ions travel at a higher velocity and
hit the detector before the heavier ions
• The “time of flight” can be used to calculate
the m/z (mass) value
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 Mass analyzers
Time-of-flight mass spectrometer

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 Mass analyzers
Time-of-flight mass spectrometer

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 Mass analyzers
Time-of-flight mass spectrometer
2
m 2t K
 2
z L
M: Mass
Z: Number of charges on ion
t: Drift time
K: Kinetic energy of ion
L: Drift length
m/z t2
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 Mass analyzers
Time-of-flight mass spectrometer
1. The ion beam enters the TOF pulsing region through a slot.
2. The applications computer sends a signal to activate the ion accelerator
and begins timing the ion flight.
3. The ion accelerator pulses, launching a “slice” of ions from the ion
stream down into the flight tube (perpendicular to the ion stream) at a
velocity which varies inversely with the square root of the mass (m/z
ratio) of the ions [v ∝ (m/z)-1/2].
4. Midway through the ion flight, the ion mirror reverses the direction of
the ions, correcting for small energy differences in the process.
5. As each ion in the “slice” reaches the multichannel plate (MCP, the
detector), it sends an electrical signal to the time to digital converter
(TDC) which records the time of detection.
6. According to a specified interval (selected so the “slices” do not overlap),
the applications computer sends another signal to the ion accelerator
and starts the sequence over again at step 2.

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 Mass analyzers
Time-of-flight mass spectrometer
High-resolution
Resolution = (Mass)/(PeakWidthHalfHeight)

Mass↑, Resolution↑

Resolution = 956.4421/0.0374
= 25,573 FWHM

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 Mass analyzers
Time-of-flight mass spectrometer
High-resolution
896.7352

598.1705 MW = 598.1705*3-3
598.1705
= 1791.5
598.5032

598.8372

599.1707
599.5064

∆m = 0.13
m = 598.1705
Resolution = 598.1705/0.13
= 22,000 FWHM 1793.4675
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400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000
m/z, amu
 Mass analyzers
Time-of-flight mass spectrometer
High-resolution

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 Mass analyzers
Time-of-flight mass spectrometer
High-resolution

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Fast scanning TOF from m/z 200-600

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 Mass analyzers
Time-of-flight mass spectrometer
High-resolution

Singly charged
~1.0 Da
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 Mass analyzers
Time-of-flight mass spectrometer
High-resolution

Doubly
charged
~0.5 Da

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 Mass analyzers
Time-of-flight mass spectrometer
High-resolution

6+ charge MW = 955.9404*6-6
~0.17 Da = 5729.6

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 Mass analyzers
Time-of-flight mass spectrometer
High-accuracy

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 Mass analyzers
Time-of-flight mass spectrometer
High-accuracy

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 Mass analyzers
Time-of-flight mass spectrometer
High-accuracy
Mass error
315.0748 = (315.0748-315.0768)/315.0768*106
= 6.3 ppm
[M+H]+

C11H12F5N2O3
Theoretical m/z = 315.0768
Measured m/z = 315.0748

220 240 260 280 300 320 340 360 380 400 420 440 460 480 500
m/z, amu 34
 Mass analyzers
Applications of Molecular MS
1: Nominal M+ peak (one m/z resolution) (or (M+1)+ or
(M-1)-) gives MW (not EI)
2: Exact m/z (fractional m/z resolution) can give
stoichiometry but not structure (double-focusing
instrument)
3: Fragment peaks give evidence for functional groups
• (M-15)+ peak → methyl
• (M-18)+ → OH or water
• (M-45)+ → CO2H
• series (M-14)+, (M-28)+, (M-42)+... → sequential CH2 loss in alkanes
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 Mass analyzers
Applications of Molecular MS
4: Isotopic peaks can indicate presence of certain
atoms, e.g. Cl, Br, S, Si
5: Isotopic ratios can suggest plausible molecules from
M+, (M+1)+ and (M+2)+ peaks
• 13C/12C = 1.08 % 2H/1H = 0.015 %
• (M+1)+ peak for ethane C2H6 should be
• (2x1.08)+(6x0.015) = 2.25% M+ peak
6: Comparison with library spectra for unknown
identification
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