1. Mass Spectrometry

2. Exact Mass Measurements
What is exact mass? m
mass of a proton: * g
mass of a neutron: * g
mass of a deuteron: * 10-24g
Avogadro’s Number (AN): * 1023
Molar mass of 2D = AN* mD = *1023* *10-24 g
= g mol-1
Carbon = 6 2D = 6* = ;
Carbon = 6(P +N) = 6( )* =
Mass of carbon = Why the discrepancy?

3. E = m C2
Where E is the energy given off from a mass discrepancy of m and C is the speed of light.
E = g* (3*1010 cm sec-1)2

5. Suppose you determined the exact mass of an ion by mass spectrometry to be 56.0377. Nominal mass 56
Using the rule of 13, the hydrocarbon formula is C4H8
Other possible molecular formulas are:
C4H8 - CH4 = C3H4O
C4H8 - CH2 = C3H6N X
C4H CH4 = C2O2 ; C4H CH4 = C2S ;
C4H CH2 = C2H4N2
C4H8 - CH4, CH2 = C2H2NO X
C4H CH2 = CH2N3 X
C4H8 - C = C3H20 X
C4H8 - CH4, 2CH2 = CN2O C4H CH2 = N4

6. Element Exact Mass 12C 12.0000 1H 1.00783 14N 14.0031 16O 15.9949
19F
28Si
31P
32S
35Cl
79Br
127I

7. The exact mass of an ion by mass spectrometry was determined to be 56
The exact mass of an ion by mass spectrometry was determined to be amu
Nominal mass exact mass
N *
CN2O *
CH2N3 …
C2O
C2H2NO
C2H4N
C3H4O
C3H6N
C4H

9. What is the origin of the peak at 141; called the P+1 peak
For a molecular formula of C9H16O, what’s the probability of having 1 13C?
Probability is (X+Y)n where X and Y is the probability of having isotope 12C and 13C, respectively and n is the number of C
(12C +13C) n =0
n = 1
n = 2
n = 3
n = 4
n = 5
n = 6
n = 7
n = 8
n = 9
(12C)9 + 9(12C)8(13C) +36(12C)7(13C)2
All 12C 1 13C C
(0.989)9 = ; 9(0.989)8(0.011)= 0.091; 36(0.989)7(0.011)2 = 0.004

10. On the basis of the molecule with only 12C = 100
Then (0.989)9 = 100(0.905/0.905) = 100 %
9(0.989)8(0.011)= 100(0.091/0.905) = 10.0 %
36(0.989)7(0.011)2 = 0.004/.905 = 0.45 %
Including 1oxygen: 17O = 0.04
18O = 0.2
P = 100 %
P+1 = %
P+2 = 0.65 %
The contribution of 2H is pretty small

11. What about
other elements?

12. Electron impact mass spectrum of CCl4

13. Single focusing instrument

17.
The quadrupole mass spectrometer consists of four precisely straight and parallel rods so arranged that the beam of ions from the ionization source of the spectrometer is directed axially between them. A voltage comprising a
a DC component and a radio frequency electric field is applied between adjacent rods, reinforcing and then overwhelming the DC field. Once inside the quadrupole, the ions will oscillate normal to the field as a result of the high frequency electric field. The oscillations are only stable for a certain function of frequency and the DC voltage; otherwise the ions will strike the rods and become dissipated. The mass range of the oscillating ions is scanned by changing the DC voltage and the frequency, keeping the ratio of the DC voltage to the frequency constant. Typical operating parameters include rf voltages of several thousand volts, frequencies in the 106 range and DC voltages of several hundred volts. Unlike a magnetic sector instrument, the mass is linear as the DC and frequency are scanned.

18. An ion trap is a combination of electric or magnetic fields that captures ions in a region of a vacuum system or tube.
A quadrupole ion trap exists in both linear and 3D varieties and refers to an ion trap that uses constant DC and radiofrequency (RF) oscillating AC electric fields to trap ions.

19. The motion of an ion is complex but it is clear that specific frequencies are involved. The frequencies can be used to manipulate the ion population in a mass selective fashion.

20. Time of Flight MS
A variety of ways can be used to create ions. Ions are not suitable for analysis for a time of flight mass spectrometer unless they are all ejected from the ion source with the same starting time. This is easy to do with a pulsed laser This results in a group of ions
which can be turned on and off during time “t” rapidly so that it only creates ions only during time “t”. The ions once formed are accelerated by a negative grid of known potential. Once accelerated, all ions have the same kinetic energy but different velocities (1/2mv2). They reach the detector at different times.

23. Formation of Ions

25. CH5+
P = 143
P +H+
P+C3H6+

26. CH5+
P = 69
P+H+
P+C3H5+

27. P = 390
Different energetics associated with different ionization methods

28. Single focusing instrument and metastable ions
Some ions are relatively unstable and fall apart shortly after being formed. If they survive long enough to be accelerated as m1+ but then fragment shortly in the field free region to m2+before encountering the magnetic field, then
Metastable Ions

29. Metastable ions: accelerated as mp+ but analyzed as md+ where mp+ > md+ , then a peak often broadened as a result of energy release accompanying decomposition, can be found at:
(md+)2/mp+
The usefulness of metastable is that they permit you to identify connectivity of fragmentation (i.e. which parent ion gave rise to which daughter ion)
Metastables are lost in instruments that use a quadruple mass filter such as in most GCMS instruments.

31. Metastables observed at m/e:
= 1602/188
131.4 = 1452/160
108.9 = 1322/160
103.7 = 1172/132
94.4 = /145
67.7 = /117

32. Fragmentation Patterns in EI MS
Electrons with 70 eV are used to bombard the sample. In addition to a molecular ion formed by loss of an electron, the resulting ions frequently have sufficient energy to fragment into daughter ions.
The easiest way to interpret fragmentation patterns is to focus on the molecular ion formed. The electron with the lowest ionization potential is lost first. Secondary reactions focus around this center.
Electrons in C-C bonds have lower ionization energies than C-H bonds.
Electrons in  bonds are easier to lose than sigma bonds.
Non-bonded electrons on heteroatoms are lost the easiest.
Conventions used in mass spectrometry means movement of 2 electrons;
 means movement of one electron

33. m/e 121: P-CH3
m/e 93: P – C3H7 68
m/e 68: P- C4H8 93
C10H16
136

34. CH2=CH-CH2-CH3
m/e 41: P –CH3 P+

35. 57
m/e 57: P – C4H9
m/e 114 parent
m/e 99: P-CH3

36. m/e 91 P - H
m/e 92 parent

37. m/e 91 P – C2H5
m/e 120 parent

38. m/e 45 P – C2H5; CHO
m/e 74 Parent
m/e 59 P – CH3

39. m/e 77: P – CHO; C2H5
m/e 106 parent
m/e 105 P - H

40. 43
m/e 58: P – C3H6
P- C2H2O
m/e 43 P- C4H9
P- C3H5O 58
m/e 100 parent
m/e 85: P – CH3 85

41. Mw 88
m/e 60: P – C2H4
P - CO 73

42. Loss of neutral molecules is frequently observed

43. m/e 83
m/e 69
MW 140
125
P-CH3

47. m/e 87 m/e 43 P-C4H9O P-C3H5O2 P-C2H4O m/e 116 P-C2H5 m/e 56 P – CH3