Bisma iqbal

M.Phil chemistry

1st semester

ASSINGMENT CH-651

Question #1

Molecular peak recognition

The highest peak at m/z 134 in the provided GC/EI-MS spectra most likely corresponds to a
molecular ion peak. The sample molecule's molar mass is 134 . Even mass implies the absence
or existence of an even number of nitrogen atoms, which must be at least two.

Base formula:
Base formula is calculated by applying rule of thirteen. Molecular weight that is 122 was divided
by 13. Remainder obtained after division equates number of carbon atoms while sum of quotient
and remainder gives number of hydrogen atoms. Base formula for given compound came out to
be C10H14.
Base peak
Base peak is assumed to have 100% intensity which is due to most stable fragment. In the
given spectrum ,base peak is at m/z 91 that is characteristic peak for tropylium cation

Signals observed m/z values Possible structures

104

91

77

65

51

39

.
Loses observed Possible radicals/neutral molecules
M-18=104 H2O
M-31=91
91-14=77

91-26=65

77-26=51
ethene molecule

Modified formula:
Since the presence of an oxygen atom is corroborated by the possibility that the peak at m/z
104 corresponds to the styrene cation as a result of 1,2-elimination from aromatic alcohol, the
revised base formula is C8H10O.

HDI
HDI= 2C+2+N-H-X/2
Putting values:

HDI=16+2-10/2 = 4

HDI is 4 that show probability of presence of a benzene ring

Possible structures
OH

1.

2-phenyl ethanaol

O
2.

benzylmethyl ether

3.

OH
2-ethyl phenol

Discussion
Structure 2 of the abovementioned probable structures is not feasible since ethers do not exhibit
the distinctive peak of M-18 caused by the loss of a water molecule,also peak at m/z 31 is
characteristic peak of methyl ethers ,generally it is base peak corresponding to methyl oxonium
ion. Additionally, structure 3 is excluded because it is phenol, which has high M-1 and M-28
peaks that correspond to hydrogen radical and CO molecule losses, respectively, but which are
not visible in the given spectrum. Phenols also exhibit a molecular ion peak as their base peak.

Therefore, the only structure that fragments in accordance with the information provided is 2-
phenyl ethanol, which proceeds through 1,2 water molecule elimination to yield peak at M-18.
For resonance stabilized tropylium cation, the base peal is at m/z 91.
Fragmentation pattern
Question # 2

Molecular peak recognition

The highest peak at m/z 115 in the provided GC/EI-MS spectra most likely corresponds to a
molecular ion peak. The sample molecule's molar mass is 115 . Odd mass implies the existence
of an odd number of nitrogen atoms, which must be at least one.

Base formula:
Base formula is calculated by applying rule of thirteen. Molecular weight that is 115 was divided
by 13. Remainder obtained after division equates number of carbon atoms while sum of quotient
and remainder gives number of hydrogen atoms. Base formula for given compound came out to
be C8H19.

Base peak
Base peak is assumed to have 100% intensity which is due to most stable fragment. In the
given spectrum, base peak is at m/z 30 that is characteristic peak for primary amines.

Modified formula
Since the presence of a nitrogen atom is corroborated by odd molecular mass and the
possibility that the peak at m/z 31 corresponds to the methyl ammonium ion that is
characteristic for primary amines ,modified formula is C7H17N.
HDI
HDI= 2C+2+N-H-X/2
Putting values:

HDI=14+2-17+1/2 = 0

HDI is zero that shows spectrum is of a saturated primary amine .

Signals observed m/z values Possible structures

100

86

72

43

30

Loses observed Possible radicals/neutral molecules

M-15=100

100-14=86

86-14=72

86-28=58

M-72=43

M-85=30

Possible structures
Fragmentation pattern

DISCUSSION
From the previously mentioned structures, structure 1, or heptanamine, correctly fragments in
accordance with the provided spectrum. Loss of 15 from the molecular ion results in the
formation of a peak of very low intensity that is visible at m/z 100; occasionally, this peak is
absent because a highly unstable cation was formed instead. This peak has homologous 14
mass unit losses that follow one another, demonstrating a straight chain alkyl group. The fact
that peaks at lower m/z values are intense because they result from secondary fragmentations
of primary cations and rearrangements further supports the existence of a straight chain alkyl
group. For example, the signal at m/z 43 indicates an isopropyl ion that is stable because it is a
secondary carbocation and goes through additional hydrogen gas loss to produce propenyl
cation, an allylic cation stabilized by resonance.
Structure 2 is also possible, but the only thing that lowers the likelihood that it is the correct
structure is because losing the methyl would result in a secondary carbocation at m/z 100,
which is predicted to generate a peak of moderate intensity, but the measured peak is of very
low intensity, pointing to the primary not secondary carbocation at this m/z.

Structure 3 is disregarded since it would have produced a base peak due to the primary
amine's beta cleavage at m/z 44, which was not seen.

QUESTION # 3

Molecular peak recognition

The highest peak at m/z 100 in the given GC/EI-MS spectra most likely corresponds to a
molecular ion peak. The sample molecule's molar mass is 100 . Even mass implies the absence
or existence of an even number of nitrogen atoms, which must be at least two.

Base formula:
Base formula is calculated by applying rule of thirteen. Molecular weight that is 100 was divided
by 13. Remainder obtained after division equates number of carbon atoms while sum of quotient
and remainder gives number of hydrogen atoms. Base formula for given compound came out to
be C7H16.
Base peak
Base peak is assumed to have 100% intensity which is due to most stable fragment. In the
given spectrum, base peak is at m/z 57 that is characteristic peak for tertiary butyl cation.

HDI
HDI= 2C+2+N-H-X/2
Putting values:

HDI=14+2-16/2 = 0

HDI is zero that shows spectrum is of a saturated hydrocarbon.

Fragments observed m/z values Possible structures

85

57

43

41

29
15

Loses observed Possible radicals/neutral molecules

M-15=85

85-28=57

57-14=43

43-14=29
Possible structures

Discussion
Because typical alkanes exhibit clusters of peaks separated by 14 amu, the given spectrum
exhibits a fragmentation pattern for saturated hydrocarbon. As a rule, fragments with two, three,
four, or even five carbons in lower mass will be more intense than those with six or more
carbons. There is a difference in intensity because of two things. The first is the general
discrimination towards higher mass components that most mass spectrometers have. Low
intensity is caused by a lack of high mass ions being captured. The greater mass fragments
usually undergo subsequent fragmentation or rearrangements, which results in the production of
the lower mass fragments.

The base peak at m/z 57 cannot be described by structure 1 of heptane based on tertiary
carbocation.

Structure 2 is broken up, producing a peak at m/z 85. This peak then loses an ethene molecule,
creating a primary carbocation at m/z 57, which cannot be the base peak and is therefore also
excluded.

The only structure that is feasible is that of 2,2-dimethyl pentane, which results from the
straightforward cleavage of a C-C single bond to generate a carbocation at m/z 85. The loss of
the ethene molecule during this carbocation's secondary fragmentation process for alkanes
causes the tertiary butyl carbocation to develop, giving rise to the base peak at m/z 57. The
most abundant fragment and most stable carbocation, the tertiary carbocation produces the
most intense peak in the mass spectrum.

The peak at m/z 43 is likewise a strong peak, because it is for a stable isopropyl cation that
passes through hydrogen gas loss to produce another intense peak at m/z 41 corresponding to
an allylic cation