Mass Spectral Interpretation Using the "Rule of '13' "

J. W. Bright'
900 Gemini Avenue, Houston. TX
E. C. M. Chen
2700 Bay Area Boulevard, Houston, TX 77058

A simnle method for the determination of ~ o t e n t i a l Data lor Substituting Some Common Elements in Organic
chemical'firmulae for a given molecular weight hasbeen de- ComDounds in Rule of 13 Calculations
veloaed in undereraduate and graduate s ~ e c t r o s c o ~iden-
ic
CIH
Element Equivalent Au -A%(M+ 1) - A ( A m ) X lo3
..
the conventional methods of mass spectral interpretation. C H,r 711 -1.1 93.90

Description of the Procedure

The procedure is based on the application of chemical logic
and is called "The Rule of '13.' " The first step in "The Rule
of '13' " is to consider only carbon and hydrogen as being
present in the molecule so the numher "13" represents the sum
of the atomic weights of one carbon atom and one hydrogen
atom. The theoretical number of carbons and hydrogens
present is found by dividing the molecular weight (MI,which
can be ohtained by locating the molecular ion in the mass
spectrum, by 13 resulting in a numerator(n) and a remain-
der(r).
MI13 = n + rI13
A hase formula for the given molecular weight which con-
sists of only carbon and hydrogen is then ohtained by appli- T h e values presented in the table for Au were obtained
cation of the formula from
C"H,,+, j ( R - 2 ) - 2C + H
AU =
2
where j is the number of atoms being added = 2 for N2.12
is obtained from the formila for HI2 and 1for the other elements presented in the table).
B is the number of bonds formed by the added atom while C
u = (n - r + 2)/2 and H are the number of carbons and hydrogens suhstraeted.
Application ol the Procedure T h e normal formula for u can also be used to calculate the
values directly.
A simple application of "The Rule of '13' "could result from
the observation of a molecular ion a t mass 78 in a mass spec- 2 C t 2 - H t j W - 2 )
11 =
trum. 2
The sum is taken over all elements except carhon and hy-
drogen.
-78 An example of the substitution process can be demon-
0 r
strated by selecting mass 142. Applying the formulae pre-
sented previously to mass 142 results in a base formula of
The hase formula is then Cs + H6+0or C6H6 from the formula C .I ., , H. ~with
. ~ zero deerees of unsaturation. Substitution of
C,H,+,. The degree of unsaturation from u = (n - r 2)/2+ t,rntr tIt.mr111. tor I . R ~ I I IIt\dru:e~n
II~. ~t.in:: initrll~atltmtrtm
+
is (6 - 0 2)/2 = 4. The formula C6Hs with four degrees of tnt 1:1r,lr rcdllt, i n thc 1%Iltrainr:
unsaturation would represent benzene provided that other
information present in the mass spectrum supported this
conclusion.
Substitution of Carbon-Hydrogen Equivalents
Chemical formulas containing elements other than carbon
and hydrogen can be ohtained by subtracting the carbon/
hydrogen mass equivalent of the element of interest from the
base formula before adding the selected element. For example,
CHdmass 16) could be replaced by oxygen(0) while CHa(mass
14) could be replaced by nitrogen(N). The table contains the
data necessary to make these substitutions, including ap-
propriate Au values for adjusting the degrees of unsaturation, I Work done in partial fulfillment of the requirements for the Master's
for some of the more common elements in organic compounds. of Science Degree.

Volume 60 Number 7 July 1983 557

The requirement for substitution of other elements for carbon elements and simply to multiply the two. For example, for a
and hydrogen could result from inspection of the mass spec- compound with C12Br3, the bromine distribution is 1:3:3:1,
trum, combustion analysis, available IRbr NMR data, etc. while that for chlorine is 961. The product is then
"The Rule of '13' "can also direct the analyst to make cer- 1 3 3 1
tain substitutions. The nitrogen rule, which simply states that 9 6 1
a single or other odd number of nitrogens in a molecule re-
quires that the molecule have an odd mass, is automatically 1 3 3 1
incorporated in "The Rule of '13' ", since an odd molecular 6 18 18 6
weight always results in a fractional value for u. Therefore, 9 27 27 9
a fractional value for u automatically indicates the presence
of a single or other odd number of nitrogens in the molecule.
The presence of oxygen and/or nitrogen is often indicated by
the calculation of a negative value of u . If one chlorine and one bromine are indicated and the mo-
Calculations for mass 74 result in a base formula of CsHla lecular weight is 190,then the base formula is C14H22 with u
with minus one degrees of unsaturation. This negative value = 4.
for u indicates that at least one oxygen or two nitrogens are U
present. Cl&z 4
-CPHII + CI +30
ClzHnCl +7
-CeH7 + Br a
CeH&IBr +4
In the undergraduate course, only C, H, ON, S, CI, and Br
Exactly which one of the above possibilities is correct could are considered. In the graduate course F, Si, P, and I are added
be determined bv close insoection of the mass soectrum or +
to the list. Also, the incremental values for the %(M 1)and
frum inspection oi1H ur hi^ data since the and<st has heen the exact masses can he calculated for the carbonlhydrogen
directed by "The Hule ot '13' " tu luuk for certain iuncrional equivalents and are included in the table. The values for the
groups. I t available IR data indicates the presence 01 a car- base quantities are given by
bonvl (characterized bs distinctive ahsor~tionin the 1580-
1900 cm-1 region) then the u value must be a t least one, and
the presence of two oxygens or one oxygen and two nitrogens
is indicated.

Tht. increments tor thrsr quant~tiesharr been calculared

and are shuwn in the table outside the duuhle lines. l i t h e M
+ 1 data are of high quality, then the number of carbon atoms
can be determined, or, if the exact mass is given, then the
presence of certain atoms can be deduced.
The presence and number of bromine and chlorine atoms Consider a compound with exact mass 162.116;the base
can generally be obtained from the isotopic distribution (M data is
+ 2,M + 4,etc.) which is given in most textbooks. Also, the
Formula u %(M + 1) Am X lot3
isotopic distribution for chlorine and bromine can be obtained
from the binomial theorem using Pascal's Triangle, which is CY~H>R 4 13.2 140
normally introduced in the discussion of proton magnetic
resonance.
'I'he use uf rhc A '(.If + 11 is uhvious and is nut illumated.
lidesired.'>!.Il + I I and $(.If s 21 can hecalc~~latrd fr~mthe
standard formulae

4 Pascal's Triangle
The relative intensities of the 79 and 81 isotopes of bromine
are nearlv. eaual
~ ~ ~~
. so the distribution can be taken from the
trianylc. Fur example, lor tour hruminei. the distrihutim 1s
I:-l:R: ( 1 . For ~,hlurinv.he distrihut~tmid the '33 i w t w e to the
37 isotope is approxi'mately 31,so the coefficientsmust be
multiplied by 3", 3"-1, etc. As an example, for n = 4, the
distribution is 1 X 81:4 X 27:6 X 9 4 X 3:l X 1 or 81:108:54:
121.
If there are mixtures of chlorine and bromine then the
easiest procedure is to obtain the distribution for each of the
These formulas are useful in distinguishing between S and Si
+
once it is noted that the %(M 2) is abnormally high.
Summary
Using "The Rule of '13'"and the table it is possible to ob-
tain all of the potential formulas for a given molecular weight
and to calculate all of the typical mass spectrometric param-
eters which are obtained experimentally. The calculated
values can then be compared to the experimental values to
obtain the most reasonable formula. Often it is necessary to
have access to IR, UV, and NMR data to make this determi-
nation.

558 Journal of Chemical Education