cee 772: instrumental methods - umass amherst · 2014-11-11 · david reckhow cee 772 #19 37 mass...
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CEE 772: Instrumental Methods in Environmental Analysis
Lecture #19 Mass Spectrometry: Basics
(Skoog, Chapt. 11, 26, 27, 28, pp.253-271, 674-693 718-721, 738-739)
David Reckhow CEE 772 #19 1
Updated: 11 November 2014
(Harris, Chapt. 23, 24 & 25) (641-664, 699-706; 742-749)
Print version
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Calibration
Concentration (µg/L)
0 5 10 15 20 25 30
Peak
Are
a
0
50
100
150
200
250
300
Sample Peak Area
Estimated Sample Concentration
Standard Curve
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Example
Number Name Retention Time (min)
1 2-Methylhexane 2.83 2 2,2,4-Trimethylpentane 3.12 3 3-Methylheptane 4.74 4 Ethylbenzen 6.69 5 m-Xylene 6.86 6 o-Xylene 7.38 7 Nonane 7.54 8 Cumene 8.07 9 1,2,4-Trimethylbenzene 9.48 10 Decane 9.59 11 Undecane 11.42 12 Naphthalene 12.96 13 1-Methylnaphthalene 15.00 14 Tetradecane 16.12 15 2,3-Dimethylnaphthalene 16.85 16 Pentadecane 17.48
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Retention Time (min)
0 2 4 6 8 10 12 14 16 18
Res
pons
e
0.0e+0
1.0e+4
2.0e+4
3.0e+4
4.0e+4
5.0e+4
6.0e+4
7.0e+4
8.0e+4
Res
pons
e0.0e+0
1.0e+4
2.0e+4
3.0e+4Solvent Blank
16-Compound Standard
1 2
3
5
4 67
8
10
9
1112
13
1415
16
Solvent
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Retention Time (min)
0 2 4 6 8 10 12 14 16 18
Res
pons
e
0.0e+0
1.0e+4
2.0e+4
3.0e+4
4.0e+4
5.0e+4
6.0e+4
Res
pons
e
0.0e+0
1.0e+4
2.0e+4
3.0e+4
4.0e+4
5.0e+4
6.0e+4
7.0e+4
8.0e+4
9.0e+4
1 2
59
Solvent
34 6
7
8
1011
1213
1415
16
Floating Product
16-Compound Standard
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Retention Time (min)
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Res
pons
e
0.0e+0
1.0e+4
2.0e+4
3.0e+4
4.0e+4
Res
pons
e
0.0e+0
1.0e+4
2.0e+4
3.0e+4
4.0e+4
5.0e+4
6.0e+4Floating Product
Soil Extract
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Mass Spectrometry
• General References on Instrument Design – Skoog, Principles of Instrumental Analysis
• 1985 (3rd ed): parts of Chapter 18 • 1991 (4th ed): parts of Chapter 18 • 1998 (5th ed): parts of Chapter 20
– Howe, Williams & Bowen, Mass Spectrometry, Principles & Applications
• 1981 (2nd ed): Chapter 1 & 12 – Loconto, Trace Environmental Quantitative Analysis
• 2001: pp356-370 – Budde, Analytical Mass Spectrometry
• 2001: parts of Chapter 1 & 2
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Use of MS with Chromatography
• Provides a 3rd dimension to chromatograms with molecular weight info
• GC/MS – Used in environ-
mental field for 20 years
• LC/MS – Newer
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Packed column GC (76 cm), isothermal using 20% Carbowax; From: Harris, 2000
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Basics of an MS instrument
• Major components
• Vacuum: 10-4 to 10-8 torr
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InletSystem
IonSource
MassAnalyzer Detector
DataSystem
VacuumPumps
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Mass Spectra
• Ethyl Benzene
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Fragmentation
• 1-decanol – A. Hard
Source
– B. Soft Source
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Interfaces
• Jet Separator
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Ion Source
• Electron Impact
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Interface & Ion Source
• Electrospray Ionization
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Mass Spectral Interpretation
• References – McLafferty, 1980; Interpretation of Mass Spectra,
3rd Ed., – University Science Books, Mill Valley, CA
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Mass Spec
• Typical reactions in electron impact
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Mass Spec
• Electron Impact – Methylene
Chloride – 1- Pentanol
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Mass Spec
• Glutamic Acid – Electron impact
• Harsh, more fragments
– Field Ionization • intermediate
– Field Desorption • Very mild, mostly molecular
ion
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Isotopic Abundances
• Elemental Signatures
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From: McLafferty, 1980
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Number of Carbon atoms
David Reckhow CEE 772 #19 20 From: McLafferty, 1980
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Abundance Chart • Isotopic Abundances
for combinations of “A+2” elements
David Reckhow CEE 772 #19 21 From: McLafferty, 1980
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From: McLafferty, 1980
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From: McLafferty, 1980
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From: McLafferty, 1980
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From: McLafferty, 1980
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From: McLafferty, 1980
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Mass Spectral Interpretation
• References – Fred McLafferty, Interpretation of Mass Spectra
• University Science Books, Mill Valley, CA – 3rd Ed., 1980 – 4th Ed., 1993 (with František Tureček)
– McLafferty & Venkataraghavan, 1982; Mass Spectral Correlations, 2nd Ed.,
– American Chemical Society, Advances in Chemistry Series #40
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From: Skoog, 1985
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From: Skoog, 1985
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From: Skoog, 1985
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Chemical Ionization • Use of reagent gas at
high pressures (0.2-2 torr) – Methane – Ammonia
• Ionize reagent gas • These ions react with
and ionize analyte – Pseudo-M ions
• M-1, M, M+1 – Adduct ions
• M+17, 29, 57
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CI: proton transfer
• Proton transfer will occur from conjugate bases of substances of lower affinity to those higher
From: Budde, 2001
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CI Spectra
• Spectra of di-isooctylphthalate
From: Howe et al., 1981, Mass Spectrometry, Principles and Applications
Methane CI
Isobutane CI
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Mass Spectral Interpretation
• References – Fred McLafferty, Interpretation of Mass Spectra
• University Science Books, Mill Valley, CA – 3rd Ed., 1980 – 4th Ed., 1993 (with František Tureček)
– McLafferty & Venkataraghavan, 1982; Mass Spectral Correlations, 2nd Ed.,
– American Chemical Society, Advances in Chemistry Series #40
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From: McLafferty, 1980
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From: McLafferty, 1980
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Mass Spectrometry • General References on Instrument Design
– Skoog, Principles of Instrumental Analysis • 1985 (3rd ed): parts of Chapter 18 • 1991 (4th ed): parts of Chapter 18 • 1998 (5th ed): parts of Chapter 20
– Howe, Williams & Bowen, Mass Spectrometry, Principles & Applications
• 1981 (2nd ed): Chapter 1 & 12 – Loconto, Trace Environmental Quantitative Analysis
• 2001: pp356-370 – Budde, Analytical Mass Spectrometry
• 2001, Oxford University Press, – parts of Chapter 1 & 2
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Mass Spectrometry
• MS – molecules are ionized and separated based on the their mass to charge ratio (m/z)
• The molecules are bombarded by electrons and the molecules release 1 or more electrons
• M + e- _> M+ + 2e-
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MS Schematic
Figure 18-1, Skoog
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MS Inlet System
• Introduce the sample to the MS • 3 types
– batch inlet – direct probe inlet – chromatographic inlet
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References • Hardy, James, http://ull.chemistry.uakron.edu/gcms/index.html, 2001 • Harris, Daniel, Quantitative Chemical Analysis,W.H. Freeman and
Company, New York, 1999 • McLafferty, F.W., Interpretation of Mass Spectra, University Science Books,
Mill Valley, CA, 1980 • Schoenberg, Ted, “The Hewlett Packard HP5890A GC/ HP5988A MS
System,” 1997 • Skoog, Douglas; Leary, James; Principles of Instrumental Analysis,
Saunders College Publishing, New York, 1992 • HP 5988A Mass Spectrometer System Hardware and Service Manual, 1985
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• To next lecture
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