1. Quantitative Chemical Analysis Seventh Edition Quantitative Chemical Analysis Seventh Edition Chapter 22 Mass spectrometry Copyright © 2007 by W. H. Freeman and Company Daniel C. Harris

4. http://webbook.nist.gov/chemistry/mw-ser.html What is mass 28? N 2 CO C 2 H 4 (ethylene) H 6 B 2 (diborane)

5. 3 step program: 1.Ionize 2.Mass select 3.detect Instrumentation

6. 2. Mass selection: Magnetic sector Quadrupole Time-of-flight (TOF) Ion trap Fourier transform ion cyclotron resonance Ion Mobility Instrumentation NB: REQUIRE VACUUM CHAMBER

7. Instrumentation – magnetic sector

8. Instrumentation - quadrupole

10. Instrumentation - TOF

11. Instrumentation – ion trap

12. Instrumentation – FT-ICR

14. Instrumentation – ion mobility

15. Instrumentation – STEP 3: detector

16. – STEP 1: Ion Source – Electron impact http://webbook.nist.gov/chemistry/mw-ser.html Standard 70 eV electron impact ionization

17. – STEP 1: Ion Source How to make elephants fly

18. – STEP 1: Ion Source - MALDI

19. STEP 1: Ion Source - ESI

21. 3 ways to get more out of a mass spectrum: 1.Isotopes (quantitation) 2.Exact mass (resolution + accuracy) 3.Fragmentation (MS/MS)

22. 1. Isotopes What does the mass spectrum of C look like?

23. 1. Isotopes What does the mass spectrum of C look like? http://www2.sisweb.com/mstools/isotope.htm

24. 1. Isotopes What does the mass spectrum of C look like? What does the mass spectrum of C 60 look like? Elemental clues from isotope distributions http://www2.sisweb.com/mstools/isotope.htm

25. 1. Isotopes What does the mass spectrum of C look like? What does the mass spectrum of C 60 look like? Elemental clues from isotope distributions Chemical clues from isotope distributions Kinetic isotope effect

26. 1. Isotopes Chemical clues from isotope distributions Water

27. 1. Isotopes Chemical clues from isotope distributions

28. 1. Isotopes What does the mass spectrum of C look like? What does the mass spectrum of C 60 look like? Elemental clues from isotope distributions Chemical clues from isotope distributions Isotope mass spectrometry

29. 1. Isotopes Isotope mass spectrometry

30. 2. Mass Accuracy Where do mass differences come from? Mass resolution m/Δm http://webbook.nist.gov/chemistry/mw-ser.html

31. 2. Mass Accuracy http://webbook.nist.gov/chemistry/mw-ser.html

32. 3. Fragmentation 1.electron impact 2.CID – collision induced dissociation 3.Electron capture 4.BIRD 5. Successive fragmentation: MS/MS/MS…

33. 3. Fragmentation http://webbook.nist.gov/chemistry/mw-ser.html Standard 70 eV electron impact ionization

34. 3. Fragmentation EI

35. 3. Fragmentation