Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA

Types of peaks:

1) Base peak Highest intensitiy peak

.
2) Molecular peak M+

3) Secondary peaks Arise from molecule-ion interactions, i.e. [M+1]+

4) Isotope peaks Due to existing isotopes and their abundancy

5) Fragment peaks Due to fragmentations and rearrangements

Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA

Molecular peak

• Ionization:
• ionized electrons: non bonding or π
• closed shell M: even number of electrons: M.+
open shell M: odd number of electrons: [M]+

• Identification: logical mass losses vs non logical losses

RADICAL LOSSES NON RADICAL LOSSES
1 H 27 C2H3 2 H2 30 CH2O
15 CH3 29 C2H5 or CHO 17 NH3 34 H2S
16 NH2 31 OCH3 or CH2H 18 H2O 36 HCl
17 OH 35 Cl 20 HF 44 CO2
19 F 45 OC2H5 or COOH 27 HCN 74 C3H6O2
26 CN 46 NO2 28 CO/C2H4 80 HBr

• Information: molecular mass and molecular formula

Rule of 13 and nitrogen rule

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http://www.chemcalc.org/mf_finder/mfFinder_em_new
Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA Molecular peak

The Nitrogen rule

Almost all molecules have an even MW (NOT 50:50 even:odd!!)

Some molecules with N have an odd mass
But not all of them…
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Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA Molecular peak

The Nitrogen rule

The N rule: Any molecule composed of C, H, N, O, Si, P, S, F, Cl, Br, I has:

• Even mass for no N or an even number of N (0,2,4,6,…)
• Odd mass for an odd number of N (1,3,5,….)
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Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA Molecular peak

The N rule: Any molecule composed of C, H, N, O, Si, P, S, F, Cl, Br, I has:

• Even mass for no N or an even number of N (0,2,4,6,…)
• Odd mass for an odd number of N (1,3,5,….)
BUT WHY?

Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA Molecular peak

The rule of 13: from a MW to a tentative molecular formula

Let’s say the molecular peak is m/z = 98

‐ 1C and 1H have an atomic mass of 13 (12 + 1).

‐Divide the m/z value by 13 to get an integer and a remainder: 98/13 = 7r7
‐ The integer equals the number of carbon atoms: 7 carbon atoms
‐ The integer plus the remainder equals the number of hydrogen atoms: 7 + 7 = 14H
‐ One possible molecular formula is C7H14
‐ If you think there's an oxygen atom in the molecule:
1 O atom has atomic mass of 16... so does 1 C atom and 4 H atoms
‐ If we add one oxygen atom to our molecular formula, we need to remove 1C and 4H
C7H14 + O ‐ CH4 = C6H10O
‐ If you think there are 2 oxygen atoms... Repeat: C6H10O + O ‐ CH4 = C5H6O2

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Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA Molecular peak

The rule of 13: from a MW to a tentative molecular formula

‐If you think there's a nitrogen atom:

1 N atom = 14 amu, equivalent to 1C + 2H
C7H14 + N ‐ CH2 = C6H12N
‐ If you think there are 2 nitrogen atoms... repeat
C6H12N + N ‐ CH2 = C5H10N2
‐ Combine if you think there are mixtures of N and O
C7H14 + O + N ‐ C2H6 = C5H8NO

These are estimates only! For exact mass to 4 decimal places you could take these possible
molecular formulae and see if any give the exact mass
* C7H14 = 98.1096
*C6H10O = 98.0732
* C5H6O2 = 98.0368
* even MW can't have odd number of N 7

Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA

Cation

Radical cation Radical

Radical cation
Neutral

Cation Cation
Radical Radical
Radical cation Radical cation

Neutral Radical cation Neutral Radical cation

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Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA

Cation

Radical cation Radical

Radical cation
Neutral

H H
H C CCH2CH3
H H

Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA

Cation
Radical
Radical cation

Neutral Radical cation

H
H N C CH3
H H

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Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA

Cation

Radical cation Radical

Neutral Radical cation

H
H N C CH3
H H

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