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Tutorial Mass Spectrometry
Tutorial Mass Spectrometry
Tutorial Mass Spectrometry
Mass spectrometry is an analytical tool that makes use of the mass to charge ratio of
particles to determine the molecular formula of a compound. In the lab, this tool can be
immensely powerful in making sure what you make is actually what you want to make.
The Theory Behind It
So what does this mass spectrometer thing look like?
that much simpler. So in order to ensure that things dont get too ionized (we only want +1
charged particles), we can put magnets that will accelerate the molecules as soon as they are
ionized, as shown in the diagram. The accelerated particles are then directed into a
magnetic field that will cause its flight trajectory to curve. The degree of curvature is
dependent on how much mass each molecular ion has. The more mass an ion has, the less
curvature its trajectory will experience. The ions then slam into a detector and its mass can
be recorded.
Reading the Spectra:
How does one go about reading all the lines on the graph? In order to read the
graph, we must first understand the basics of the graph itself. The x-axis of our graph is the
mass-to-charge ratio (m/z for short), and because the charge of the ions is 1, our mass-tocharge ratio will be simply mass divided by 1, or more simply put our mass. The y-axison
the other handis the relative ion abundance of our molecule at different weights.
Relative abundance means that the abundances are based off of the most prevalent ion,
not how many ions there are in total. Now that we know what the graph means, how do
we find M, M+1 and M+2 from our spectra? See below.
2-Hexene: 6 carbons, but only 12 hydrogens. Presence of double bond reduces number of
hydrogens by two
Cyclohexane: 6 carbon, but only 12 hydrogens. Presence of ring structure reduces number
of hydrogens by two.
When taking into account the number of hydrogens, we also have to consider that
each nitrogen will increase the maximum number of possible hydrogens by 1. So if there is
one nitrogen in a 4 carbon formula, then the maximum possible number of hydrogens
becomes 11 instead of 10 (as predicted by the 2n + 2 formula). With all of these
considerations, we get the general formula:
Max number of hydrogens + halogens = 2C + N +2
This is referred to as the hydrogen/halogen rule.
Putting It All Together
So with everything covered up until this point, we have taken into account the
number of carbons and the presence or absence of sulfurs, chlorines, bromines, fluorines,
and iodines. We can subtract these masses from the total mass of the molecule (M) to get
the mass that the nitrogens, hydrogens, and oxygens account for, and with that, formulas
can be proposed. Just remember to check the validity of formulas with the nitrogen and
hydrogen/halogen rules.
Implications?
Weve gone through all this trouble simply to learn to derive possible formulas from
looking at mass spectra. Admittedly, this gives us a good deal of information regarding the
composition of atoms within the molecules, but is that all? Of course not! With the
molecular formula, it is possible to reveal more about the structure. Here, we introduce the
concept of the double bond equivalent (DBE). This is essentially a unit defined as two
hydrogens less than the maximum number of hydrogens possible in the structure. For
example, two DBEs means that there are four less hydrogens than possible in the formula.
If you remember back to the bit about the hydrogen rule, youll see that each DBE implies
the presence of either a double bond or a ring. When it comes to determining structure,
this bit of information can be extremely useful.
So to calculate DBEs, we can use a variation on the hydrogen/halogen rule formula.
DBE = C H/2 + N/2 + 1
Now just a few more reminders. DBEs can only come in whole and positive
numbers. Any negative or fraction DBE is an indication that you should probably recheck
your formula and recalculate the DBE. Best of luck!
References
http://www.chemistry-reference.com/images/ballstick/hexane.png
http://0.tqn.com/d/chemistry/1/0/D/U/1/2-hexene.png
http://upload.wikimedia.org/wikipedia/commons/c/c6/Cyclohexane-chair-3D-balls.png
http://www.google.com/imgres?q=mass+spectra+of+bromopropane&um=1&hl=en&biw=1050&
bih=683&tbm=isch&tbnid=SIm1w9cG74fEyM%3A&imgrefurl=http%3A%2F%2Fandromeda.ru
tgers.edu%2F%7Ehuskey%2F335f11_lec.html&docid=kqsqvBLU5n4cM&imgurl=http%3A%2F%2Fnewark.rutgers.edu%2F%7Ehuskey%2Fimages%2Fmass_spe
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