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A Guide to Solving Mass Spectroscopy Problems

Useful Vocab:
Mass Spectroscopy - study and application of mass spectra, aka relative ion abundance vs
charge
* we use it to find possible molecular formulas
M - the molecular ion composed of isotopes with the lowest mass numbers
* this means that hydrogen = 1, carbon = 12, chlorine = 35, etc
M+1 - molecular ion whose mass is one higher than M
* uses isotopes like H=2, C=13, etc as long as masses add up to one more than M
M+2 - molecular ion whose mass is two higher than M
Nitrogen Rule - when M is even, the number of nitrogens in the molecule is even (including 0),
and when M is odd, the number of nitrogens is odd
H-rule - the maximum number of monovalent (Hydrogen, Halogen) atoms for a given number of
carbons and nitrogens is:
H = 2C + N + 2
* if there are 5 carbons and 1 nitrogen, then it cant have more than 13 H
m/z - ratio of an ions mass (amu) to its formal charge, units not usually included
Now that the definitions are out of the way, here is the step by step process of analyzing data:
Step 1) Look at M.
a) M = the molecular mass, which we will use for calculations
* if M is NOT 100%, then we need to make it 100% while keeping the ratios of
M+1 and M+2 to M intact
b) Use nitrogen rule ( if odd: # of N is odd; if even, # of N is even)
Step 2) Look at M+1
a) take the M+1 percentage and divide by 1.1%
* this gives us the number of carbons
* if number has a decimal, then the number of carbons has two options, we must
accept both (ex, if we get 6.3, then the # of carbons could be 6 OR 7)
Step 3) Look at M+2
a) this is where we look for other elements, namely S, Cl, and Br
b) thresholds we need to know:
* Sulfur: ~4%
* Chlorine: 33%
* Bromine: 99%
c) if number is <4%, then we assume that none are present

* although the threshold for chlorine could also indicate sulfur, we generally
assume only the element with the larger threshold is the only one present
Step 4) Calculate available amu
a) by this point weve found out the possible number of carbons, possible larger
elements so now we need to calculate the available amu for hydrogens, oxygens, and nitrogens
b) remember that we have two options for the number of carbons, so we need to
consider two scenarios for possible chemical formulas
c) general formula: M - (# carbons x 12) = available amu
* if sulfur/chlorine/bromine is present, subtract is out as well
Step 5) Trial and Error
a) using available amu, determine number of oxygens, nitrogens, and hydrogens
b) tables would be helpful:
Oxygens

Nitrogens

Hydrogens

Formula

c) keep in mind the number of nitrogens to make sure it doesnt violate the nitrogen rule
Step 6) Lather, rinse, repeat
a) use step 5 again for the the other possible # of carbons
Step 7) Elimination
a) eliminate all formulas that violate the H-rule
* even if the formula seems unlikely, like C11O, it technically doesnt violate the
rule so it must be considered anyway
Example:
M: m/z = 164 (100%)
M+1: m/z = 165 (4.62%)
M+2: m/z = 166 (100%)
Step 1) M
a) M= 164 amu, this is our mass
b) 164 is even, so the # of nitrogens is even
Step 2) M+1
a) 4.62%/1.1% = 4.2
* this means 4 OR 5 carbons present
Step 3) M+2
a) 100%: this indicates Bromine is present
Step 4) Calculate available amu

a) 4 carbons: 164 - (12*4) - (1*79) = 37 amu


b) 5 carbons: 164-(12*5) - (1*79) - 25 amu
Step 5)
* four carbons
Oxygens
Nitrogens
0
0
0
2

Hydrogens
37
9

Formulas
C4H37Br
C4H9BrN2

Is it okay?
NO, violates H-rule
fine

21

C4H21BrO

no, violates H-rule

C4H5BrO2

fine

Hydrogens

Formula

Is it okay?

Step 6)
* five carbons
Oxygens
Nitrogens
0

25

C5H25Br

No, violates H-rule

C5H9BrO

fine

* note in order to have nitrogens, two must be present and 25 amu doesnt allow for that
Step 7)
Acceptable formulas: C5H9BrO, C4H9BrN2 , C4H5BrO2

Works Cited:
Example came from: Dr. Hardingers Thinkbook
definitions came from: Illustrated Glossary on website
Lecture Supplement