EXPERIMENT NO.

NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY

Name: Chariezza Le J. Sanglad

Student No.: 2015-00925

Name: Erlindo Regala

Student No.: 2015-01947

Name: Leziel Talpis

Student No.: 2015-01076

ABSTRACT
 INTRODUCTION

Nuclear magnetic resonance spectroscopy, most commonly known as NMR spectroscopy,

is a research technique that exploits the magnetic properties of certain atomic nuclei. This type of

spectroscopy determines the physical and chemical properties of atoms or the molecules in which

they are contained. It relies on the phenomenon of nuclear magnetic resonance and can provide

detailed information about the structure, dynamics, reaction state, and chemical environment of

molecules. The intramolecular magnetic field around an atom in a molecule changes the resonance

frequency, thus giving access to details of the electronic structure of a molecule and its individual

functional groups.

The principle behind NMR is that many nuclei have spin and all nuclei are electrically

charged. If an external magnetic field is applied, an energy transfer is possible between the base

energy to a higher energy level (generally a single energy gap). The energy transfer takes place at

a wavelength that corresponds to radio frequencies and when the spin returns to its base level,

energy is emitted at the same frequency. The signal that matches this transfer is measured in many

ways and processed in order to yield an NMR spectrum for the nucleus concerned.

Figure 1. Block Diagram for NMR Spectroscopy

 The nuclei of many elemental isotopes have a characteristic spin (I). Some nuclei have

integral spins (e.g. I = 1, 2, 3 ....), some have fractional spins (e.g. I = 1/2, 3/2, 5/2 ....), and a few

have no spin, I = 0 (e.g. 12C, 16O, 32S, ....). Isotopes of particular interest and use to organic

chemists are 1H, 13C, 19F and 31P, all of which have I = 1/2. Since the analysis of this spin state

is fairly straightforward, discussion of nmr will be limited to these and other I = 1/2 nuclei.

When a nucleus with I = 1/2 is placed in a magnetic field, it can either align itself with the

field (lower energy) or against it (higher energy). If radio waves are applied, nuclei in the lower

energy state can absorb the energy and jump to the higher energy state. Observation is either the

absorption of energy, or the subsequent release of energy as the nucleus "relaxes" back to the lower

energy state. Traditionally this was done by scanning slowly through a range of radio wave

frequencies (this is called continuous wave, CW). However, this has largely been replaced by the

faster Fourier Transform (FT) method where one big, broad pulse of radio waves is used to excite

all nuclei, then the results are analyzed by computer.

NMR spectra are unique, well-resolved, analytically tractable and often highly predictable

for small molecules. NMR analysis is used to confirm the identity of a substance. Different

functional groups are obviously distinguishable, and identical functional groups with differing

neighboring substituents still give distinguishable signals. A disadvantage is that a relatively large

amount, 2–50 mg, of a purified substance is required, although it may be recovered through a

workup. Preferably, the sample should be dissolved in a solvent, because NMR analysis of solids

requires a dedicated MAS machine and may not give equally well-resolved spectra. NMR is not

suitable for observing fast phenomena, producing only an averaged spectrum. Although large

amounts of impurities do show on an NMR spectrum, better methods exist for detecting impurities,

as NMR is inherently not very sensitive - though at higher frequencies, sensitivity narrows.
 METHODOLOGY

In nuclear magnetic resonance, the sample was cited in the center of a cylinder inside the

probe of an NMR instrument. The magnet was the super conductive one was located inside the

cylindrical metal casing and it was cold to 4 K in a jacket of liquid helium, which was cited in a

jacket of liquid nitrogen at 77 K. The magnet used a current of 50 amperes which started to flow

continuously as the coils have 0 resistance of 4 K. The radio signals were generated by electronics.

The samples were placed in a machine and was removed by the Auto-changer which takes the

sample into from the carousel. Furthermore, a proton spectrum of ethanol was run. Small amount

of ethanol was taken and dissolved in dichloromethane in which all of the hydrogen atoms were

replaced by deuterium. These showed that the signal from a hydrogen atom in a solvent would not

be mixed up with those of the sample.

Tetramethylsilane was added as a reference, each molecule of this has 12 hydrogen atoms

all exactly in the same environment. The signal was taken as 0 of a spectrum and has a value of 0

ppm. Inside the instrument, the flow of nitrogen and the spinning of sample was controlled by the

plastic spinner. The spinner was placed in a tube in such a position the sample is in the center of a

magnetic field when it was in the NMR instrument. Together these ensures that the sample

experienced a uniform magnetic field. The sample was placed in the auto changer and the identity

was predicted, as well as the position in the carousel it is in. The correct sample was selected and

placed in NMR instrument. Under the control of a computer, the instrument applied several

typically 16 pulses of radio waves to the sample and the responses called resonances were

collected . These resonances were sum up by the computer and was process to give a spectrum that

takes about 5-10 minutes.

 RESULTS AND DISCUSSION

The figure below shows the NMR Spectrum of Methyl propanoate.

q t
s
o
q t

Figure 2. NMR Spectrum of Methyl propanoate

The NRM spectra of methyl propanoate, C3H8O2, is seen in the above figure . Formed

from the Fisher esterification of methanol and propanoic acid, this ester is a four-carbon molecule

with a characteristic carbonyl group adjacent to an oxygen atom within the main carbon chain.

Due to the great shielding of the TMS protons, this signal is the zero standard from the chemical

shift and degree of deshielding of the other signals are measured. The three signals that directly

illuminate the structure of methyl propanoate are the triplet centered at 1.090 ppm (3 H), the quartet

centered at 2.280 ppm (2 H), and the singlet ceneterd at 3.620 ppm (3 H). The presence of these

three signals confirm that there are three different groups of nonequivalent hydrogens in methyl

propanoate.
 The signal that occurs at around 1.090 ppm in methyl propanoate. The number and 1:2:1

relative heights of the three peaks within this signal confirm the presence of a triplet. This triplet

represents the hydrogen molecules that are found in the –CH3 methyl group at the left end of the

carbon chain. The expected H NMR range for such an alkyl hydrogen is within 0.9 to 1.5 ppm, a

range which included the 1.090 ppm value actually observed. Since this methyl group is not in

contact with any strongly electronegative groups, the amount of deshielding is the lowest for these

hydrogens than any other hydrogen type in methyl propanoate. This signal is split into three peaks,

indicating that the adjacent carbon only has two hydrogens bonded to it, as is true of the adjacent

–CH2 group that is only close enough to affect the absorbance of the three alkyl hrdrogens under

study.

This second type of hydrogen shows itself in the H NMR spectrum of methyl propanoate

further downstream than the alkyl hydrogen’s already analyzed. This is consistent with the more

electronegative chemical environment around this hydrogen type, which results in a greater degree

of deshielding. For any hydrogen’s bound to a carbon adjacent to a carbonyl group, the predicted

H NMR signal is around 2.1 to 2.2 ppm. The value observed in the spectrum above is just slightly

higher than the accepted chemical shift, which can be attributed to the slight electronegative,

deshielding effect of the oxygen atom further down the carbon chain. The carbon adjacent to the

–CH2 group, which is the methyl group at the left end of the chain, contains three hydrogens. The

value of N in this case is assigned to be 3 adjacent equivalent protons, so that the –CH2 hydrogen

signal will be split into a quartet in accordance with the N + 1 rule. This quartet also follows the

1:3:3:1 area ratio predicted by Pascal’s triangle.

This final signal is the furthest downstream, and thus the most deshielded hydrogen type,

in the H NMR spectrum of methyl propanoate. The oxygen adjacent to this left end –CH3 group
creates the most electronegative chemical environment, typically showing a signal in the 3 to 4

ppm range. As seen above, the 3.620 ppm chemical shift value is consistent with this accepted

range. Its place at the higher end of this range may be due to the slight deshielding that possibly

results from the carbonyl group two positions to the right on the main carbon chain. Furthermore,

this signal is a singlet with only one peak, meaning that signal splitting does not occur. After all,

this hydrogen type is too great a distance from and is, thus, not coupled with any other

nonequivalent hydrogens.
SUMMARY AND CONCLUSION
APPENDICES
 REFERENCES

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