Chapter 12 - Mass Spectrometry
Determination of the Structure of Organic Compounds
- a variety of methods apply, mainly using specialized instruments
- spectroscopy - absorption of light of various wavelengths
(Chaps 13 & 14)
- "wet" methods - inferences from specific chemical
reactivity
- comparisons with known samples or databases
Mass Spectrometry
- sample converted to a beam of ions ( usually +, sometimes
- )
- fragmentation of ionized molecules may take place
- fragments are collected by mass ( actually mass/charge ratio,
but charge is usually +1 )
- original structure is deduced from
- parent molecular ion (without fragmentation)
- fragments and their abundance
Instrumental Operation
- various ways of generating ions from a sample
- EI - electron ionization - high-energy beam of electrons
knock electrons off the sample molecules
- CI - chemical ionization - uses gas-phase reactions like
proton transfer
- FAB - fast atom bombardment - also knocks out electrons by
impact
- MALDI - matrix-assisted laser desorption ionization - laser
blasts ions out of a matrix (solid)
- magnetic field causes deflection of the ions as they travel
- bends them into a curve
- light ions (low m/z) are deflected most
- heavy ions are deflected less
- mass analyzer - the ions are spatially sorted by m/z and
detected as an ion current
Mass Spectrum
- a plot of ion current observed as the detector scans over
m/z values
- base peak - highest intensity peak (usually assigned intensity
100)
- parent molecular ion ( M+ or just M )
- corresponds to the original molecule missing one electron
- correlates with the molecular weight
- low-resolution MS - detects integer m/z values ( ±
1 )
- high-resolution MS - capable of identifying m/z to ±
0.0001
- e.g., CO and N2 both have MW = 28
but differ at high resolution
Isotopes
- some elements have distinctive isotope patterns in their
natural abundance
- C consists of 98.9% C-12 and 1.1 % C-13
- a compound with 20 C would give an M+1 peak about 22% the
size of M
- Br consists of about 50% each of Br-79 and Br-81 (atomic
weight ~ 80)
- a compound with one Br would have M and M+2 peaks about equal
in size
- Cl consists of about 75% Cl-35 and 25% Cl-37
- a compound with one Cl would have M and M+2 peaks in about
3:1 ratio
Fragmentation Patterns
- initial ionization generates a radical ion by loss of one
electron
- loss of a bonding electron may lead to bond breakings
- different functional groups often have characteristic fragmentation
patterns
Interpretation of Mass Spectra
- compounds containing only C, H, O, S, halogen, will always
have M even
- an even (m/z) corresponds to a radical ion
- an odd (m/z) corresponds to a carbocation
- the nitrogen rule - compounds with one N (or an odd number
of N) will have M odd
- a significant sized M+2 peak can indicate Br, Cl, or S (depending
on intensity)
- alkanes tend to fragment C-C bonds that give more
stable cations or radicals
- alkenes usually show a strong M+, fragment at allylic
bonds (forms allyl cations)
- alkynes usually show a strong M+, fragment at propargylic
bonds
- alcohols fragment easily, losing H2O
or breaking an alpha C-C bond (forms oxonium ion)
- PRACTICE with spectra to learn how to visualize the information
they contain