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 8. Atomic Mass Spectrometry

Prof. Ke Xu

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Homework due 2/22 in class

Skoog:
6-7, 6-14, 6-15, 8-5, 9-13, 10-8

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Questions
Q1: In AA, how to address chemical interferences due to formation of compounds?
How about due to ionization?

Q2: What source is most often used to generate AE? How does it achieve low
chemical interference?

ICP (nductively Coupled Plasma)

High temperature good atomization
High density of electrons in plasma suppressed ionization

Q3: Why is a high-resolution monochromator particularly useful for AE but not AA?

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Multichannel

ICP Source
Grating
Entrance
Slit

Mirror Arc/Spark Source

Photomultipliers Detector at different position

Multiple channels

Fixed positions of slits + multiple PMTs

Useful for quick measurement of a few
preset lines/elements
Computer
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Comparison of different methods

(ppb)

low detection limit, more sensitivity.

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The many lines in AES

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Mass spectrometry (MS) of elements

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Much fewer spectroscopy lines!
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Mass spectrometry (MS) Removing an electron from the molecule

Direct measurement of the mass (often mass-to-charge ratio, m/z) of ions from
atoms and molecular fragments.

Results readily interpreted

Detection of multiple elements at the same time
High throughput
Low interference
High sensitivity / low detection limit
High cost ICP-AES; 100 ppm cerium

Better method
ICP-MS
10 ppm cerium
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MS: implementation

Vacuum: 10-5 to 10-8 torr

Vacuum range Pressure in mbar Molecules / cm3 Mean free path

Ambient pressure 1013 2.7 1019 68 nm
Low vacuum 300 1 1019 1016 0.1 100 m
Medium vacuum 1 103 1016 1013 0.1 100 mm
High vacuum 103 107 1013 109 10 cm 1 km
Ultra high vacuum 107 1012 109 104 1 km 105 km
Extremely high vacuum <1012 <104 >105 km
How long does a molecule has to travel before hitting another molecule? Mean free path

Note: 1 mbar 0.75 Torr

Ion source for atoms: ICP!

Skimmer

ICP does produce positive ions

Differential pumping: coupling low vacuum (ICP) to high vacuum (MS)
Sample cone, skimmer cone: ion beam passes through orifices at center. Non-
co-linear particles are pumped out.
Acceleration by electric fields (voltage differences) It is easier to accelerate charged particle

In MS: mass analyzer (discussed later) + detector 11

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Detectors

Faraday cup converts the striking ion

into a current

Similar to photomultiplier, but using electron instead of photon

Electron multiplier: cascade

of electrons results in a 106
amplification of current
Atomic MS
data
Isotopes!
Same number of protons
(thus electrons and
chemical properties), but
differ in neutron number
Fixed relative distribution

Hg

Still much fewer lines

when compared to AE!
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ICP-MS data

Spectroscopy interferences
Isobaric interference: same atomic weight of isotopes of different elements: 40Ar+
vs. 40Ca+,
Polyatomic ion interference: ArH+, O2+
Oxide and hydroxide species: CaO+, CaOH+

Correction:
Use alternative isotopes for measurement to avoid overlapping
Subtraction basing on other isotopes 14
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Qualitative and semi-quantitative applications

Usually exist in mixture

Example: rare earth sample.

Extremely hard for AES!
Quantitative applications

Linear signal-concentration
relationship over large range
Good performance
Internal standards sometimes
used
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Mass analyzer: Quadrupole mass filter 17

Band-pass filter for m/z!

Passes resonant ions; non-resonant ions hits rod and removed (loose charge)
Quadrupole: band-pass filter

Different
combinations
of dc and ac
potentials in
XZ and YZ
planes

Heavier ions are less affected by the ac potential and respond to the dc potential of the rods.
X-Z: the positive dc potential repels (positive) ions. Heavy ions are thus focused by the dc.
Light ions respond to ac and hit rods. Thus a high-pass mass filter.
Y-Z: (positive) ions are attracted by the negative dc potential. Heavy ions hit rods. Light ions
respond to ac field and are kept at the center. Thus a low-pass mass filter.
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Quadrupole filter as a mass analyzer for MS
Quadrupole is a band-pass filter. How to obtain spectrum?

Scan m/z to obtain spectrum!

Mass range: up to 3,000 MS resolution:
Resolution: m ~ 1 m/m ~ 2,000
Good for atomic MS! 19
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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