4) Each Nitrogen: Increases the max H count by one and each F, Cl, Br, and I

5) Max number of Hydrogens and Halogens: =2C + N + 2

6) F and I: Are absent unless otherwise stated
7) MW - (mass due to C,S, Cl, Br, F, and I) = mass due to O, N, and H
8) The nitrogens and oxygens will vary in number and the nitrogen and hydrogen-halogen rule
can help eliminate candidates
9) Cannot round the carbon atoms that are found due to M+1/1.1. This could eliminate
reasonable structures
Practice Problems of Thinkbook(PG 122):
7) Use the M and M+1 data to determine the molecular formula in each case. Unless otherwise
stated, assume that carbon, hydrogen, oxygen and nitrogen are the only elements present.
a) M: m/z = 148 (100%); M+1: m/z = 149 (11.25%)
b) M: m/z = 164 (100%); M+1: m/z = 165 (4.62%); contains bromine
c) M: m/z = 149 (100%); M+1: m/z = 150 (11.3%)
d) M: m/z = 150 (100%); M+1: m/z = 151 (11.52%)

a) Step 1: The first thing we look at is if m/z of M is even or odd. In this case it is even and we
know that there will be an even number of Nitrogens
Step 2: The relative abundance of M is 100%, thus the relative abundance of M+1/1.1% gives
the approximate number of carbon atoms in the molecular formula.
11.25/1.1= 10.2; 10 or 11 carbons because we do not know for certain which it is and
canceling out possibilities could lead in eliminating reasonable structures
Step 3: Mass (M) - mass (C) = mass (N, O and H) This will give us the mass due to the other
atoms present and help us to further figure out the molecular formula
148(M:m/z)-120(C10)=28 amu for N, O and H for carbon 10
148(M:m/z)-132(C11)=16 amu for N, O and H for carbon 11
Step 4: Construct a table that gives the possible options for the possible number of nitrogen and
oxygen atoms in the formula. Recall that we will have an even number of nitrogens. Also recall
the Hydrogen/Halogen Rule(H-Rule) that states the max number of hydrogens + halogens = 2C
+ N + 2. Additionally we will be using the lowest mass of the isotopes for the molecules.
The number of Oxygen and Nitrogen atoms chosen has to do with the mass of N,O and H that we
found
Carbon 10
Oxygens Nitrogens 28-O-N = H Formula Notes
0 0 28-0-0 = 28 C10H28 Violates H-Rule; 2(10)+0+2=22
1 0 28-16-0 = 12 C10H27 Reasonable
0 2 28-0-28 = 0 C10N2 Reasonable although unlikely
Carbon 11
Oxygens Nitrogens 16-O-N = H Formula Notes
0 0 16-0-0=16 C11H16 Reasonable
1 0 16-16-0=0 C11O Possible but unlikely

b) Step1: Is the m/z of M even or odd? In this case it is even and thus there will be an even
number of Nitrogens. Also keep in mind that there is Bromine to account for when calculating
mass of N,O and H.
Step 2: The relative abundance of M is 100%, thus the relative abundance of M+1/1.1% gives
the approximate number of carbon atoms in the molecular formula.
4.62/1.1=4.2; 4 or 5 carbons because we do not know for certain which it is and
canceling out possibilities could lead to the elimination of reasonable structures
Step 3: Mass(M)-Mass(C)-Mass(Br)=mass(N,O and H) This will give us the mass due to the
other atoms present and help us to further figure out the molecular formula
164(M:m/z)-48(C4)-79(79Br) =37 amu for N,O and H for carbon 4
164(M:m/z)-60(C5)-79(79Br) = 25 amu for N,O and H for carbon 5
Step 4: Construct a table that gives the possible options for the possible number of nitrogen and
oxygen atoms in the formula. Recall that we will have an even number of nitrogens. Also recall
the Hydrogen/Halogen Rule(H-Rule) that states the max number of hydrogens + halogens = 2C
+ N + 2. Additionally we will be using the lowest mass of the isotopes for the molecules. Also
there will be one bromine present in the molecular structure.
Carbon 4
Oxygens Nitrogens 37-O-N = H Formula Notes
0 0 37-0-0=37 C4H37Br Violates the H-Rule
1 0 37-16-0=21 C4H21Br Violates the H-Rule
2 0 37-32-0=5 C4H5Br Reasonable
0 2 37-0-28=9 C4H9Br Reasonable
Carbon 5
Oxygens Nitrogens 25-O-N = H Formula Notes
0 0 25-0-0=25 C5H25Br Violates H-Rule
1 0 25-16-0=9 C5H9Br Reasonable

c) Step 1: Is the m/z of M even or odd? In this case it is odd and thus there will be an odd
number of Nitrogens.
Step 2: The relative abundance of M is 100%, thus the relative abundance of M+1/1.1% gives
the approximate number f carbon atoms in the molecular formula.
11.3/1.1= 10.3 10 or 11 carbon atoms, do not eliminate possibilities
Step 3: Mass (M) - mass (C) = mass (N, O and H)
149(M) - 120(C10) = 29 amu for N,O and H for carbon 10
149(M) - 132(C11) = 17 amu for N,O and H for carbon 11
Step 4: Construct a table and remember that this time the Nitrogen count is odd
Carbon 10
Oxygens Nitrogens 29-O-N = H Formula Notes
0 1 29-0-14=15 C10H15N Reasonable
Carbon 11
Oxygens Nitrogens 17-O-N = H Formula Notes
0 1 17-0-14=3 C11H3N Reasonable

d) Step 1: The m/z of M is even and thus the nitrogen count is even
Step 2: The relative abundance of M is 100%, thus the relative abundance of M+1/1.1% gives
the approximate number f carbon atoms in the molecular formula
11.52/1.1=10.5 10 or 11 carbon atoms, do not eliminate possibilities
Step 3: Mass (M) - mass (C) = mass (N, O and H)
150(M) - 120(C10) = 30 amu for N, O and H for carbon 10
 150(M) - 132(C11) = 18 amu for N, O and H for carbon 11
Step 4: Construct a table and remember that the nitrogen count is even
Carbon 10
Oxygens Nitrogens 30-O-N = H Formula Notes
0 0 30-0-0 = 30 C10H30 Violates the H-Rule
1 0 30-16-0 = 14 C10H14O Reasonable
0 2 30-0-28 = 2 C10H2N2 Reasonable
Carbon 11
Oxygens Nitrogens 18-O-N = H Formula Notes
0 0 18-0-0 = 18 C11H18 Reasonable
1 0 18-16-0 = 2 C11H2O Reasonable

8) What can be concluded about the molecular structure of an unknown compound from the
following mass spectrum: M has relative intensity of 100%, M+1 = 7.85%, M+2 = 0.0023%?
Step 1: What information are we given: By listing what we know we can draw conclusions
and figure out portions of the structure based on the information given
-The relative intensity of M is 100% thus M+1/1.1 will give us the number of
carbons that we will have in the molecular formula
7.85/1.1 = 7.14, this implies that there are either seven or eight carbons
-The percentage given for M+2 is very small. This corresponds to a small peak
because the percentage shows the intensity and from the intensity percentages of sulfur, 4%,
chlorine, 33%, and bromine, 100%, the percent given for intensity is too small to contain any of
these atoms and thus none are present.
-However due to the limited information we cannot conclude the number of nitrogen,
oxygen or hydrogen. For this we would need the M, which reveals the mass of the molecule
composed of the lowest mass isotopes.

References

Google Images

Hardinger, Steven. Chemistry 14C: Organic Molecular Structures and Interactions: PowerPoint
Lectures for Chemistry 14C with PowerPoint CD. Plymouth, MI: Hayden-McNeil, 2012. Print.

Hardinger, Steven. Chemistry 14C: Structure of Organic Molecules : Course Thinkbook :

Concept Focus Questions, OWLS Problems, Practice Problems. Plymouth, MI: Hayden-McNeil,
2012. Print.