Professor Qin Rohith Narra

Section 003 11-28-21

Excedrin Analysis Using Proton NMR Prelab

Proton NMR is a technique which exploits the fact that a hydrogen atom has a nuclear spin
which responds to an external magnetic field. When acted by an external magnetic field, the proton’s
spin is aligned with the field and flips back to its original state when the external field is removed. In this
process, energy is released and could be translated into a signal on the NMR spectrum. The location of
the peak depends on the environment of each proton due to shielding effects such as withdrawing of
electron density in the presence of electron withdrawing groups. The choice of solvents in NMR
experiments are deuterated solvents as deuterium has no spin and will not respond to an external field
which prevents extra peaks other than the sample peaks. Even in deuterated solvents, there will be
trace amounts of deuterated species with hydrogens instead of deuterium which corresponds to a small
peak but is easy to separate from the rest of the spectrum. In a previous lab, we used the HPLC
technique to separate and quantify the constituents of an Excedrin tablet but will be using proton NMR
instead to achieve the same goal in this lab. The components in our sample which we are interested in
separating and quantifying are caffeine, aspirin, and acetaminophen. Their structures are shown below:

Figure 1. Caffeine Figure 2. Acetaminophen Figure 3. Aspirin

Caffeine will have three separate singlet peaks corresponding to three protons per peak with no signal
splitting as each set of unique protons are not directly neighboring. In acetaminophen, there will be five
peaks – triplet peak corresponding to alcohol hydrogen, triplet peak corresponding to the two
hydrogens on carbons directly connected to the alcohol carbon, triplet peak corresponding to the
hydrogens connected to remaining two ring carbons, singlet peak corresponding to amine carbon, and
singlet peak corresponding to the three methyl hydrogens. Aspirin will have six peaks – two singlet
peaks, one doublet peak, and three triplet peaks.

References:

(1) “Analysis of Excedrin Migraine Tables by Proton NMR” (handout supplied by Dr. Qin)