ادڤانس د.تغريد 2

The unit mass of the molecular ion of C7H7NO is m ∕ z 121—that is, the sum of the
unit masses of the most abundant isotopes: (7 × 12 [for 12C]) + (7 × 1 [for 1H]) + (1
× 14 [for 14N] + (1 × 16 [for16O]) = 121.
OR
 In addition, molecular species exist that
contain the less abundant isotopes, and
these give rise to the “isotope peaks” at
M+1,M+2, etc.
In this Figure, the M+1 peak is approximately
8% of the intensity of the molecular ion peak,
which for this purpose, is assigned an intensity
of 100%.
Copyright © 2023 to Assist. Prof. Tagreed N-A Omar ,Pharmacy College, University of Baghdad. All Rights Reserved.
If only C, H, N, O, F, P, and I are present, the approximate expected
percentage (M + 1) and percentage (M + 2) intensities can be
calculated by use of the following equations for a compound of
formula CnHmNxOy
(note: F, P, and I are monoisotopic and do not contribute and can be
ignored for the calculation):
% (M+1) ≈ (1.1 • n) + (0.36 • x) % (M+2) ≈ (1.1 • n)2∕200 + (0.2 • y)
• If these isotope peaks are intense enough to be measured accurately, the

above calculations may be useful in determining the molecular formula.
• If sulfur or silicon is present, the M+2 peak will be more intense. In the case
of a single sulfur atom, 34S contributes approximately 4.40% to the M+2
peak; for a single silicon in the molecule, 30 Si contributes about 3.35% to
the M+2 peak.
• Mass spectrometers are capable of separating & detecting
individual ions even those that only differ by a single atomic mass unit.
• So amolecules containing different isotopes can be distinguished.
• This is most apparent when atoms such as bromine or chlorine are
present (79Br : 81Br, intensity 1:1 and 35Cl : 37Cl, intensity 3:1) where peaks at
"M" and "M+2" are obtained.
• molecular ion peak is diff. from a M+2 peak by 2 halogen.
• The intensity ratios in the isotope patterns are due to the natural abundance
of the isotopes.
• "M+1" peaks are seen due the presence of 13C in the sample.
For Easily Recognized

Elements in MS
Halides
Bromine : M+ ~ M+2 (50.5% 79Br /49.5% 81Br)
Chlorine : - M+2 is ~ 1/3 as large as M+
Iodine : * I+ at 127 * Large gap F – presence of M-19 fragments
 A single chlorine atom results in a contribution of 32.50% to the
M+2 peak, while a single bromine atom contributes 98.00% to the
M+2 isotope peak. The effect of several bromine and chlorine atoms
is described in Section 1.6.16. Note the appearance of additional
isotope peaks in the case of multiple bromine and chlorine atoms.
 Obviously the mass spectrum should be routinely scanned for the
relative intensities of theM+2,M+4, and higher isotope peaks, and
the relative intensities should be carefully measured. Since F, P, and I
are monoisotopic, they can be difficult to spot.
Table below lists the principal stable isotopes of the common elements and their relative
abundance calculated on the basis of 100 molecules containing the most common isotope
(IHD)
also known as double bond equivalents (DBE) or the degree of unsaturation,
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Copyright © 2023to Assist. Prof. Tagreed N-A Omar ,Pharmacy College, University of Baghdad. All Rights Reserved. 8
The index of hydrogen deficiency can be calculated for compounds
containing carbon(n), hydrogen (m), halogen(x),nitrogen (y),
oxygen(z), and sulfur having the generalized molecular formula,
CnHmXxNyOz,
i.e: C7H7NO
Index = (n) − (m∕2) − (x∕2) + (y∕2) + 1 same to
IHD=IV-I/2+II/2+1
IHD = 7 – 7/2 + ½ + 1
IHD = 8-3.5 + 0.5…….. IHD =5
Note that divalent atoms (oxygen and sulfur) are not counted in the
formula.
Benzene ring +( = or ring)
Of course, other isomers

(i.e., compounds with the
same molecular formula)
are possible.
“Polar” structures must be used for compounds containing an atom in
a higher valence state, such as sulfur or phosphorus.
 Thus, if we treat sulfur in dimethyl sulfoxide(DMSO) formally as a
divalent atom, the calculated index,0, is compatible with the
structure in Figure 1.12. We must use only formulas with ﬁlled
valence shells; that is, the Lewis octet rule must be obeyed.
FIGURE 1.12 “Polar” Lewis structures of dimethyl sulfoxide, nitromethane, and

triphenylphosphine oxide that correctly account for the index of hydrogen
deﬁciency.
 The formula above for the index can be applied to fragment ions as well
as to the molecular ion.
 When it is applied to even-electron (all electrons paired) ions, the result
is always an odd multiple of 0.5. As an example, consider C7H5O+ with an
index of 5.5. A reasonable structure is:
 Since 5.5 pairs of hydrogen atoms would be necessary to obtain the

corresponding saturated formula C7H16O (CnH2n+2O). Odd-electron
fragment ions will always give integer values of the index. Such simple
considerations give the chemist very ready information about structure.
 As another example, a compound containing a single oxygen atom might

quickly be determined to be an ether or a carbonyl compound simply by
the degree of hydrogen deficiency. Much of the potential structural
information is readily confirmed with information from IR and NMR
spectra
The “Rule of Thirteen” can be used to identify possible
Molecular formulas for an unknown hydrocarbon, CnHm.
The rule of 13 states that the formula of a compound is a
multiple n of 13 (the molar mass of CH) plus a remainder r.
Step 1: n = M+ /13 [ integer only, use remainder (R) in step2 ] C

Step 2 : m = n + remainder from step 1 H
Example: The formula for a hydrocarbon with M+ =106 can be found :

Step 1: n = 106 / 13 = 8 ( r = 0.153 * 13 = 2 )
Step 2: m = 8 + 2 = 10 106 / 13 = 8.153
Formula: C8H10
• If a heteroatom is present,
– Subtract the mass of each heteroatom from the MW
– Calculate the formula for the corresponding hydrocarbon
– Add the heteroatoms to the formula.
Or It Contain 2 heteroatoms as O
Another method:
Q. / A compound gives a mass spectrum with peaks at m/z =
77 (40%), 112 (100%), 114 (33%), and essentially no other
peaks. Identify the compound.
First, your molecular ion peak is 112 and you have a M+2 peak at 114.
Therefore, you have a halogen.
 Now, your molecular ion peak and M+2 peak are in a 3 to 1 ratio.
This means chlorine.
 So, 112 - 35 = 77 ( C & H )
 C’s 77/12 = 6 carbons
 6 x 12 = 72
 77 – 72 = 5
 C6H5Cl. IHD=6 - (5H+1Cl)/2+1=
 =7-3=4
Copyright © 2023to Assist. Prof. Tagreed N-A Omar ,Pharmacy College, University of Baghdad. All Rights Reserved. 9
Sigma Cleavage Example : Hexane
,1
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4
5
Primary alcohols, m/z CH2=OH m/z =31
examples +
Primary amines, m/z CH2=NH2 + m/z =30
CH3
CH3 - +
c l e a va g e CH3 - CH- CH 2 • + CH2 = NH2
CH3 - CH- CH 2 - C H 2 - N H 2
m/z 30
6
– Radical Site Driven
 Cleavage is caused when an electron from a bond to an atom

adjacent to the charge site pairs up with the radical.
Weakened α-sigma bond breaks This mechanism is also
called α- cleavage
 The charge does not move in this reaction.
 Charged product is an even electron species
 α-cleavage directing atoms: N > S, O, π, R• > Cl, Br > H
 Loss of longer alkyl chains is often favored
 Energetics of both products (charged and neutral) are important
8 8
2. Heterolytic cleavage: Charge Driven Also known as
inductive cleavage
 Charged site induces a pair of electrons to migrate from an adjacent
bond or atom (this breaks a sigma bond)
 Fragmentation by movement of two electrons:
In this type of cleavage both the electrons of the bond are taken over by
one of the atoms; the fragments are an even electron cation and a radical
with the positive charge residing on the alkyl group. (the charge
migrates to the electron pair donor .
So the electron pair neutralizes the original charge
 It is designated by a conventional arrow (↶ or ↷) to signify the
transfer of a pair of electrons in the direction of the charged site.
 Even electron fragments can further dissociate by this mechanism .
 Inductive cleavage directing atoms
9
10

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The unit mass of the molecular ion of C7H7NO is m ∕ z 121—that is, the sum of the

% (M+1) ≈ (1.1 • n) + (0.36 • x) % (M+2) ≈ (1.1 • n)2∕200 + (0.2 • y)

• If these isotope peaks are intense enough to be measured accurately, the

For Easily Recognized

Iodine : * I+ at 127 * Large gap F – presence of M-19 fragments

also known as double bond equivalents (DBE) or the degree of unsaturation,

Index = (n) − (m∕2) − (x∕2) + (y∕2) + 1 same to

Of course, other isomers

FIGURE 1.12 “Polar” Lewis structures of dimethyl sulfoxide, nitromethane, and

 Since 5.5 pairs of hydrogen atoms would be necessary to obtain the

 As another example, a compound containing a single oxygen atom might

Step 1: n = M+ /13 [ integer only, use remainder (R) in step2 ] C

Example: The formula for a hydrocarbon with M+ =106 can be found :

 Cleavage is caused when an electron from a bond to an atom

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