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Spring 2017 CHEMISTRY 105

Instrumental Methods in Analytical Chemistry


Lecture: MW 9 AM 10 AM 219 Dwinelle
Labs: MTuWTh 1 5 PM 305 Latimer

Lecture 9. Mass Spectrometry -Analyzers

Prof. Ke Xu

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Questions
Q1: Why are atomic MS data cleaner and easier to interpret than AES?
Each metals only have a few lines of isotopes

Q2: What gives rise to the 35.5 relative atomic mass of Cl?

Natural abundance: ~ of 35Cl + ~ of 37Cl

Q3: What are the major components of MS?

Vacuum

Q4: What mass analyzer is most often used for atomic MS?

Quadrupole: band-pass filter for mass

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Quadrupole: band-pass filter

Heavier ions are less affected by the ac potential and respond to the dc potential of the rods.
X-Z: A high-pass mass filter.
Y-Z: A low-pass mass filter.
Mass range up to 3,000
Resolves single atomic mass unit 3
Time-of-flight (TOF)

10-7 sec typical

Detect m/z by the time of flight: heavier ions fly slower!


No scanning needed: fast
High transmission: most of the injected ions are detected
Unlimited mass range (useful for very large molecules)
Need to generate ions in a pulse (e.g., laser): distribution of start time
Lower resolution (~300): distribution of velocity.
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Reflectron time-of-flight mass spectrometer

Corrects for chromatic aberration: The more energetic ions penetrate deeper
into the reflectron, and take a slightly longer path to the detector
Also doubles the flight path for the same length of vacuum!
Resolution ~1,500
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Electromagnet analyzer (magnetic sector): old school

Force
due to B

Centripetal
force

KE due to acceleration
voltage

Mass-to-
charge ratio

Ions with different m/z bend differently in field!


Heavier ions bend less (larger r)
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Electromagnet analyzer as a mass analyzer for MS 7

Multichannel detection Scanning

Multichannel detection vs. scanning of V and/or B


Medium mass range: up to ~10,000
Massive and expensive
Resolution <~2,000 with one magnetic sector: energy distribution and
directional distribution due to ion source
Double-focusing system

Narrows down the energy distribution and directional


distribution due to ion source!
ESA: band-pass for kinetic energy. Electric field: fast
ions hit upper electrode; slow ions hit lower electrode.
Magnetic analyzer: analyzes m/z for very narrow
energy distribution.
Achieves resolution of 2,500+ 8
Quadrupole ion trap

Trap + release

Ions of different m/z are first all stored inside the trap.
By raising the RF potential, the trajectories of ions of successive m/z values are made
unstable and ejected out of the trap and detected. Scan to obtain spectrum!
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Fourier transform ion cyclotron resonance (FTICR)

Angular velocity

Detect m/z from cyclotron frequency! Heavier lower frequency


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FTICR: demo

https://nationalmaglab.org/education/magnet-academy/learn-the-basics/stories/what-s-in-an-oil-drop

http://www.youtube.com/watch?v=7EHngA4S3Ws
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FTICR for MS

High resolving power (105+)


Very high accuracy
Very high masses (record: unit mass
resolution at 112 kDa)
Attomole detection limits
Massive and expensive
FTICR

Massive and expensive


High magnetic field
from superconductive
coils

11.5 Tesla FTICR 13

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