MASS SPECTROMETRY

FRAGMENTATION PATTERN OF
HYDROCARBONS
(ALKANES AND CYCLOALKANES)

DEPARTMENT OF
CHEMISTRY
CONTENTS
 MASS SPECTROMETRY:-
“MASS SPECTROMETRY IS AN
INSTRUMENTAL TECHNIQUE IN WHICH
SAMPLE IS CONVERTED TO RAPIDLY
MOVING POSITIVE IONS BY ELECTRON
BOMBARDMENT AND CHARGED
PARTICLES ARE SEPARATED ACCORDING
TO THEIR MASSES.”
 MASS SPECTRUM:-
• MASS SPECTRUM IS A PLOT OF RELATIVE ABUNDANCE AGAINST THE RATIO OF
MASS/CHARGE (M/Z).

PRINCIPLE BEHIND MASS SPECTRA:-

 TO MEASURE RELATIVE MOLECULAR MASS.
 TO KNOW THE FRAGMENTATION OF MOLECULES.
 COMPARISON OF MASS SPECTRA WITH KNOWN COMPOUNDS.
BASIC PRINCIPLE:-
 ELECTRON BOMBARDMENT:-
• THE IMPACT OF A STEAM OF HIGH ENERGY ELECTRONS CAUSES THE MOLECULE TO LOSE
AN ELECTRON FORMING A RADICAL CATION.
 RADICAL CATION IS A SPECIE WITH POSITIVE CHARGE AND ONE UNPAIRED ELECTRON.
• THE IMPACT OF THE STREAM OF HIGH ENERGY ELECTRONS CAN ALSO BREAK THE
MOLECULE OR THE RADICAL CATION INTO FRAGMENTS.
 LOSS OF ELECTRON:-
ELECTRO
N
BOMBAR
DMENT

Radical Fragment Fragment

Loss
Cation ation ions
of e

e⁻
M M•⁺ + E⁻ C
ati
15 ev on
Radic
al

Fragments
70 Neutral Radical
molecul
ev e
Cation
 EJECTED ELECTRON:-
• IN THE HIGHEST POTENTIAL ENERGY MOLECULAR ORBITAL.
• HELD LEAST TIGHTLY TO THE MOLECULE.
• FROM NON BONDING ORBITAL, N.
• REMOVAL OF ELECTRON FROM PI ORBITAL IS EASY THAN SIGMA ORBITAL.

EXAMPLES:-
 FRAGMENTATION PROCESSES:-

FRAGMENTATION IS A TYPE OF CHEMICAL DISSOCIATION.

FRAGMENTATION TAKE PLACE BY A PROCESS OF HETEROLYSIS

OR HOMOLYSIS.
DEFINITION:-
“AN EXTREMELY USEFUL RESULT OF ELECTRON IMPACT
IONIZATION IN PARTICLE IS A PHENOMENON KNOWN AS
FRAGMENTATION”
THE RADICAL CATION THAT IS PRODUCED WHEN AN ELECTRON IS KNOCKED OUT OF A
NEUTRAL CLOSED-SHELL MOLECULE IN EI-MS INITIALLY POSSESSES A LOTS OF ENERGY.
ENERGY SUFFICIENT TO BREAK CHEMICAL BOND, RADICAL CATION WILL USUALLY BREAK
INTO NEUTRAL RADICAL AND A CATION.
PEAKS WITH SMALLER M/Z VALUES CALLED FRAGMENT ION PEAKS REPRESENT POSITIVELY
CHARGED FRAGMENTS OF MOLECULE.
 BACKGROUND:-

• MASS SPECTROMETRY USES HIGH ENERGY ELECTRONS TO BREAK A MOLECULE INTO

FRAGMENTS.
• SEPARATION AND ANALYSIS OF THE FRAGMENTS PROVIDES INFORMATION ABOUT:

STRUCTURE
MOLECULAR WEIGHT
 EXPLANATION:-

• BOMBARDMENT OF MOLECULES BY AN ELECTRON BEAM WITH ENERGY 15 EV USUALLY

RESULTS IN THE IONIZATION OF MOLECULES BY REMOVAL OF ONE ELECTRON (MOLECULAR
ION FORMATION).
• WHEN THE ENERGY OF ELECTRON BEAM IS INCREASED BETWEEN 50-70EV, THESE
MOLECULAR IONS ACQUIRE A HIGH EXCITATION RESULTING IN THEIR BREAK DOWN INTO
VARIOUS FRAGMENTS. THIS PROCESS IS CALLED FRAGMENTATION PROCESS.
 FRAGMENTATION PATTERNS:-
• THE IMPACT OF THE STREAM OF HIGH ENERGY ELECTRONS OFTEN BREAKS THE MOLECULE
INTO FRAGMENTS, COMMONLY A CATION AND A RADICAL.
 BOND BREAK TO GIVE THE MOST STABLE CATION,
 STABILITY OF THE RADICAL IS LESS IMPORTANT.

STEVENSON’S RULE:-
THE MOST PROBABLE FRAGMENTATION IS THE ONE THAT LEAVES THE POSITIVE CHARGE ON
THE FRAGMENT WITH THE LOWEST IONIZATION ENERGY.
FRAGMENT IONS ARE FORMED BY MEANS OF UNIMOLECULAR PROCESSES (PROCESSES
LEADS TO FORMATION OF MORE STABLE IONS ARE MOST FAVORABLE).

MLOECULAR IONS:-
1. ODD ELECTRON IONS (OE•⁺) HAVE EVEN MASS
2. EVEN ELECTRON IONS (EE⁺) HAVE ODD MASS
 CLEAVAGE OF BOND:-
• MOST COMMON FRAGMENTATION INVOLVES ONE BOND CLEAVAGE.
• ODD ELECTRON ION (OE•⁺) AN FRAGMENT IN TWO WAYS:-
1.CLEAVAGE OF BOND TO CREATE :
EE⁺
RADICAL
2. CLEAVAGE OF BOND TO CREATE:
OE•⁺
NEUTRAL MOLECULE
• EVEN ELECTRON ION (EE⁺) CAN ONLY FRAGMENT ON ONE WAY:- (CALLED EVEN-ELECTRON
RULE)
CLEAVAGE OF BOND TO CREATE:
EE⁺
NEUTRAL MOLECULE
 RADICAL SITE INITIATED CLEAVAGE:-Α CLEAVAGE
 ONE BOND CLEAVAGE.
 THE BOND BROKEN IS NOT ATTACHED TO RADICAL SITE BUT TO THE NEXT NEIGHBOURING
ATOM.(Α CLEAVAGE).
 IT IS FRAGMENTATION OF OE⁺ ONLY.
 OCCUR AT SATURATED OR UNSATURATED SITES.
 CHARGE SITE INITIATED CLEAVAGE:- INDUCTIVE
CLEAVAGE
 ONE BOND CLEAVAGE.
 REPRESENTED BY SYMBOL I.
 INVOLVES THE ATTRACTION OF ELECTRON PAIR BY AN ELECTRONEGATIVE HETEROATOM
THAT ENDS UP AS A RADICAL OR NEUTRAL MOLECULE.
 OPERATE ON BOTH OE⁺ AND EE⁺.
 TWO BOND CLEAVAGE:-
• IN THIS PROCESS, AN ELIMINATION OCCUR, AND ODD MOLECULAR ION YIELDS AN OE⁺
AND AN EVEN ELECTRON NEUTRAL FRAGMENT N (USUALLY WATER, HX OR ALKENES).

RETRO DIELS-ALDER CLEAVAGE:-

• UNSATURATED SIX-MEMBERED RINGS CAN UNDERGO RETRO DIELS-ALDER
FRAGMENTATION.
• IT YIELDS RADICAL CATION AND NEUTRAL ALKENES.
 MCLAFFERTY
REARRANGEMENT:-
• IT INVOLVES TRANSFER OF HYDROGEN ATOM ON A CARBON 3 ATOMS AWAY FROM THE
RADICAL CATION OF AN ALKENE, ARENE, CARBONYL, OR IMINE TO A CHARGE SITE BY SIX-
MEMBERED TRANSITION STATE, WITH CLEAVAGE OF SIGMA BOND BETWEEN Α AND Β
POSITIONS.
 SATURATED HYDROCARBONS:
STRAIGHT CHAIN COMPOUNDS:-
FOLLOWING ARE THE FEATURES OF THE MASS SPECTRA OF ALKANES:

• THE RELATIVE MASS OF THE PARENT PEAK DECREASES AS THE

MOLECULAR MASS INCREASES IN THE HOMOLOGOUS SERIES.
• THE MOLECULAR ION PEAK IS NORMALLY PRESENT. (NORMALLY
WEAK)
• THE SPECTRA GENERALLY CONSIST OF CLUSTERS OF PEAKS
SEPARATED BY 14 MASS UNITS CORRESPONDING TO DIFFERENT CH2
GROUPS.
.
 BRANCHED CHAIN HYDROCARBONS:-

• GREATER THE BRANCHING IN ALKANES LESS IS THE APPEARANCE OF THE MOLECULAR ION
AND IF IT APPEARS, INTENSITY WILL BE LOW.
• BOND CLEAVAGE TAKES PLACE PREFERABLY AT THE SITE OF BRANCHING. DUE TO SUCH
CLEAVAGES, MORE STABLE SECONDARY OR TERTIARY CARBOCATION RESULTS.
• GREATER NUMBER OF FRAGMENTS RESULTS FROM THE BRANCHED CHAIN COMPOUND
COMPARED TO STRAIGHT CHAIN. THIS IS DUE TO GREATER PATHWAYS AVAILABLE FOR
CLEAVAGE.
 ALKANES:-
THE GENERAL RULES FOR ALKANES ARE:
• THE RELATIVE HEIGHT OF THE MOLECULAR ION PEAK IS GREATEST FOR STRAIGHT CHAIN
MOLECULES AND DECREASES AS THE BRANCHING INCREASING.
• THE RELATIVE HEIGHT OF THE MOLECULAR ION PEAK DECREASES WITH CHAIN LENGTH FOR
HOMOLOGOUS SERIES.
• CLEAVAGE IS FAVORED AT ALKYL-SUBSTITUTED CARBONS, WITH THE PROBABILITY OF
CLEAVAGE INCREASING AS THE SUBSTITUTION INCREASES.
• BRANCHED ALKANES TEND TO FRAGMENT FORMING MOST STABLE CARBOCATIONS.
• FRAGMENTATION SPLITS OFF SIMPLE ALKYL GROUP;

Loss of Loss of Loss of Loss of

Methyl Ethyl Propyl Butyl
M⁺- 15 M⁺ -29 M⁺- 43 M⁺- 57
 EXAMPLES:-
STRAIGHT CHAIN ALKANES:-
MASS SPECTRUM OF HEXANE:-
 BRANCHED CHAIN ALKANES:-
MASS SPECTRUM OF 2-METHYLPENTANE:-
MASS SPECTRUM OF 2-METHYLBUTANE:-
MASS SPECTRUM OF 2-CHLOROPROPANE:-
MASS SPECTRUM OF 2,2 DIMETHYLBUTANE:-
 CYCLOALKANES:-
• THE FRAGMENTATION PATTERN OF CYCLOALKANES SHOWS MASS CLUSTERS ARRANGED IN A
HOMOLOGOUS SERIES, AS IN ALKANES.
• GENERALLY, SHOWS STRONG MOLECULAR ION PEAKS.
• FRAGMENTATION OF RING COMPOUNDS REQUIRES THE CLEAVAGE OF TWO CARBON-
CARBON BOND.
• MOST SIGNIFICANT MODE OF CLEAVAGE OF CYCLOALKANES INVOLVES THE LOSS OF ETHENE
(CH2=CH2).
• THE PEAK RESULT FROM LOSS OF ETHENE FROM PARENT MOLECULE IS MORE INTENSE IN
SPECTRUM.
• WHEN CYCLOALKANES BEARS A SIDECHAIN, LOSS OF SIDE CHAIN IS FAVORABLE DUE TO
FORMATION OF SECONDARY CARBOCATION.

Loss of Ethene
M-28
MASS SPECTRUM OF CYCLOHEXANE:-
MASS SPECTRUM OF METHYL CYCLOPENTANE:-
MASS SPECTRUM OF ETHYL CYCLOHEXANE:-
EASE OF FRAGMENTATION:-
 FACTORS THAT IMPACT FRAGMENTATION:-
1.ENERGETIC FACTOR:
 RELATIVE BOND STRENGTH

C-CL> C-BR>C-I
 STABILITY OF CATIONS OR RADICALS

2. KINETIC FACTOR:
 AVAILABILITY OF FAVORABLE CYCLIC TRANSITION STATE
QUESTIONS OR COMMENTS