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 can’t have more than 13 “H”

m/z - ratio of an ion’s 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 we’ve 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 doesn’t 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 doesn’t 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 Hydrogens Formulas Is it okay?
0 0 37 C4H37Br NO, violates H-rule
0 2 9 C4H9BrN2 fine

1 0 21 C4H21BrO no, violates H-rule

2 0 5 C4H5BrO2 fine

Step 6)
* five carbons
Oxygens Nitrogens Hydrogens Formula Is it okay?

0 0 25 C5H25Br No, violates H-rule

1 0 9 C5H9BrO fine

* note in order to have nitrogens, two must be present and 25 amu doesn’t allow for that

Step 7)
Acceptable formulas: C5H9BrO, C4H9BrN2 , C4H5BrO2

Works Cited:

Example came from: Dr. Hardinger’s Thinkbook

definitions came from: Illustrated Glossary on website

Lecture Supplement