LABORATORY REPORT OF SPECTROSCOPY

( CHM 3402 )

Name : Lai Sok Fuen

Matric No : 110484

Partner’s Name : Tan May Thing

Matric No : 110123

Programme : Bacelor Sains ( Kepujian ) – Chemistry

Expt.Tittle : Nuclear Magnetic Resonance Spectrometer

No.Expt : 8

Date : 13/1/2004

Demo : Masnizaayu Abd.Manaf, Chen Lai Min

Lab : MP4
Experiment 8: Nuclear Magnetic Resonance Spectrometer

Objectives:

1. To understand the basic concept of NMR spectroscopy

2. To know the basic components/part of NMR spectrophotometer and their
functions.
3. Confirm the possible structures for the sample given from chemical shifts and the
number of protons represent by each peak.
4. To determine completely the structure of an unknown molecule.

Introduction:

Nuclear magnetic resonance (NMR) is a spectroscopic method that is even more

important to the organic chemist than infrared spectroscopy. Many nuclei may be studied
by NMR techniques, but hydrogen and carbon are most commonly available. Whereas
infrared spectroscopy reveals the types of functional groups that present in a molecule,
NMR gives information about the number of magnetically distinct atoms of the type
being studied. When hydrogen nuclei (protons) are studied, for instance, one can
determine the number of each of the distinct types of hydrogen nuclei as well as obtain
information regarding the nature of the immediate environment of each type. Similar
information can be determined for the carbon nuclei. The combination of IR and NMR
data is often sufficient to determine completely the structure of and unknown molecule.

The chemical shift and shielding

Nuclear magnetic resonance (NMR) has great utility because not all protons in a
molecule have resonance at the same frequency. This variability is due to the fact that the
protons in a molecule are surrounded by electrons and exits in slightly different electronic
environment from one another, the valence-shell electron densities vary from one proton
y to another. The protons are shielded by the electrons that surround them. In an applied
magnetic field, the valence electrons of the protons are caused to circulate. This circulate,
called a local diamagnetic current, generates a counter magnetic field, which opposes the
applied magnetic field. Figure 8.1 illustrates this effect, which is called diamagnetic
shielding or diamagnetic anisotropy.

Circulation of the electrons around a nuclear can be viewed as being similar to the
flow of an electric current in an electric wire. From physics, we know that the flow of a
current through a wire induces a magnetic field. In an atom, the local diamagnetic current
generates a secondary, induced magnetic field, which has a direction opposite that of the
applied magnetic field.
 Figure 8.1: Diamagnetic anisotropy – the diamagnetic shielding of a nuclear
caused by the circulation of valence electrons.

As a result of diamagnetic anisotropy, each proton in a molecule is shielded from

the applied magnetic field to an extend that depends on the electron density surrounding
it. The greater the electron density around a nucleus. The greater the induced counter
field that opposes the applied field. The counter field that shields a nucleus diminishes
the net applied magnetic field that the nucleus experiences. As a result, the nucleus is at a
lower frequency. This means that it also absorbs radiofrequency radiation at this lower
frequency. Each proton in a molecule is in a slightly different chemical environment and
consequently has a slightly different amount of electronic shielding, which results in a
slightly different resonance frequency.

The continuous-wave(CW) instrument

Figure 8.2: Schematically illustrates the basic elements of a classical 60-MHz

NMR spectrometer. The sample is dissolved in a solvent containing no interfering
protons(usually CCl4 or CDCl3),and a small amount of TMS is added to serve as an
internal reference. The sample cell is a small cylindrical glass tube that is suspended in
the gap between the faces of the pole pieces of the magnet. The sample is spun around its
axis to ensure that all parts of the solution experience a relatively uniform magnetic field.

Figure 8.2: The basic elements of the classical nuclear magnetic resonance
spectrometer.
 Also in the magnet gap is a coil attached to a 60-MHz radio frequency (RF)
generator. This coil supplies the electromagnetic energy used to change the spin
orientations of the protons. Perpendicular to the RF oscillator coil is a detector coil. When
no absorption of the energy taking place, the detector coil picks up none of the energy off
the RF ascillator coil. When the sample absorbs energy, however, the reorientation of the
nuclear spins induces a radiofrequency signal in the plane of the detector coil and the
instrument responds by recording this as a resonance signal or peak.

At constant field strength, the distinct types of the protons in a molecule precess
at slightly different rates. Rather than changing the frequency of the RF oscillator to
allow each of the protons in a molecule to come into resonance, the typical NMR
spectrometer uses a constant-frequency RF signal and varies the magnetic field strength.
As the magnetic field strength is increased, the precessional frequencies of all the protons
increase. When the precessional frequency of a given type or proton reaches 60-MHz,it
has resonance. The magnet that is varied is actually a two-part device. There is a main
magnet, with strength of about 1.41 Tesla, which is capped by electromagnet pole pieces.
By varying the current through the pole pieces, the worker can increase the main field
strength by as much as 20 parts per million(ppm).Changing the field in this way
systematically brings all of the different types of protons in the sample into resonance.

Chemical environment and chemical shift

If the resonance frequencies of all protons in a molecule were the same, NMR
would be of little use to the organic chemist. Not only do different types of protons have
different chemical shifts, but each also has a characteristic value of chemical shifts. Every
type of protons has only a limited range of δ values over which it gives a clue as to the
type of proton originating the signal, just as an infrared frequency gives a clue as to the
type of bond or functional group. It is important to learn the ranges of chemical shifts
over which the most common types of protons have resonance. Figure 8.3 is a correlation
chart contains the most essential and frequency encountered types of proton.

Figure 8.3: A simplified correlation chart for proton chemical shift values.
Methodology:

The given sample is weighted and put inside the NMR tube.

0.5ml solution and tetrametilsilane-TMS 1% are put into the NMR tube to dissolve the
sample. Make sure that the volumes of sample come to minimum volume that is 0.5ml or
35mm.

Mop the NMR tube to make sure it is in dry condition.

The spectrometer has to standard with 5%TMS and 35% chloroform before used
it.

The NMR tube with the sample inside it is put into the probe that has been prepared.

The spectrum of NMR sample has been obtained.

The integration of each peak has been measure by measuring the height of the peak.

The integration relative for the peaks have been compare, and expected the sum of the
protons for every peak.

The chemical shift for every peak is marked.

According to the data that we get, the structure of the sample can be obtained.

Result and the analysis data:

A) The spectrum of the sample A/COCl3

δ/ppm The data that we get

0.000 TMS
7.336 Doublet peak. There is 2-atom hydrogen, which is
7.302 neighbour to each other at one-C aromatic ring.
7.021 This is the peak for the solvent.
6.974 Singlet peak. There has no neighbour to the atom-H
at C-aromatic ring.
3.861 Singlet peak.
3.775
2.606

The formula molecule for sample A is:C10H1203

While, the value of the reference, δ(TMS) = 0.00ppm

The proposed structure for the sample A is as below:

There are 2 readings for doublet peak in the spectrum for the part (a) and (b). They
are at 7.336ppm and 7.302ppm. According to the (n+1) rule, n+1=1+1=2.This mean that
part (a) and (b) are neighbour for each other. By this, there occurred a doublet peak at this
range. The H proton bonded to the benzene ring give the reading of 6.974ppm. It has no
neighbour with hydrogen atom, thus according to the (n+1) rule, n+1=0+1=1, so there is
only a peak in the spectrum, it is a singlet peak foe the part(c).

As for the part (d), (e) and (f), they have no neighbour which contain proton H. So,
they give only a singlet peak. The electronegative effect from the carbonyl group, C=O
produced deshielded effect and this will cause the chemical shift move to the lower field
which is to the left side. The reading for the part (d), (e) and (f) is 3.861ppm, 3.775ppm
and 2.6061ppm respectively. Actually, it is found that each carbon atom bonds three
protons. But, because of the chemical vibration, it gives only one peak, which is high as a
group. The peak for the chemical shift 2.325ppm, shown clear here, but we can’t
determine it. This maybe cause by the contamination of the solution.

B) The spectrum for sample B/COCl3

δ/ppm The data that we get
0.000 TMS
1.138 Triplet peak. There is a proton from CH3 which
1.257 possesses 2 neighbours.
1.377
2.039 The methyl group has no proton nearby singlet peak.
3.961 Quartet peak. The proton from CH2 which is equivalent
4.078 gives one peak that gives 3-proton neighbour.
4.197
4.317

The formula molecule for sample B is: C4H802

While, the value of the reference, δ(TMS) = 0.00ppm

The proposed structure for the sample B is as below:

The TMS absorption for this sample B is shown at δ = 0.00ppm.There are 3 types of
proton which shown with 3 peaks in the spectrum.

The peak consist of a set of triplet peak at δ = 1.138,1.257 and 1.377ppm. As for the
singlet peak, that is at δ = 2.039ppm and for the quartet peak are at δ = 3.961, 4.078,
4.197 and 4.317ppm.

The part (a) is the triplet peak. We found that the spin coupling occurred and the
proton of CH3 give a peak in the spectrum. The proton for CH 3 has two neighbour, so by
using the (n+1) rule, (n+1) = 2+1=3, there were 3 peaks we can see. A chemical shift
occurred for this triplet peak.

There is a methyl group that has no H proton for the singlet peak. According to the
(n+1) rule, (n+1)=0+1=1, means that is only one peak (singlet) there. The chemical shift
for the methyl group in part(c) is greater than the methyl group in part (a). This is because
the methyl group in part (c) is bonded to the carbonyl group, C=O which is a group has a
strong electronegative effect that can cause the CH3(c) move to the lower field.

For quartet peak, there is a peak produced from the CH2 group of (b). The 2 protons
from CH2 are equivalent and there are 3-proton neighbour nearby which are the hydrogen
from CH3 group (a). So, by using the (n+1) rule, (n+1) = 3+1= 4,therefore the quartet
peak is produced.

Discussion:
 Nuclear Magnetic Resonance (NMR) Spectroscopy is the studied of the molecular
structure through the measurement of the interaction of radio-frequency electromagnetic
radiation with a collection of nuclei immersed in a strong magnetic field. NMR is the first
method of structure determination organic chemists turn to provide a map of carbon-
hydrogen framework of an organic molecule. This involved measuring the absorption of
radiofrequency radiation by a material placed in a strong magnetic field. Many nuclei
may be studied, but H and C are most commonly available.

The spectrum NMR that we used is spectrum NMR proton ( 1H). Spectrum NMR
will show out the series of peak. The wide of each peak is linear with the number of
proton where it is represent by the integrator. The wide of the peak is measured by the
pengamir electronic, which will show a series, which is related to the certain absorption,
or we called it kamiran curve. Ratio, height step will give different ratio nucleus proton in
the compound.

Not every nucleus 1H or in the molecule will absorb the energy radio frequency, rf at
the same frequency. The entire nucleus is surrounding by the electrons. When they come
to the outside magnet field, they will form their own magnet field. This magnet field is
contrary with the outside magnet field, so that this field is effective for the nucleus to
become smaller. By this, we can say that nucleus is shielded.

Every nucleus in the compound is in the different electronic surroundings, so

shielding for every nucleus is different, and this mean that effective magnet field is not
the same for every nucleus. This differentiate can be observe through the NMR
spectroscopy, and we can see this signal for every C or H in the compound.

The spectrum NMR is given in the chart to show the strength field is increased from
left to the right. So, the left side of the chart is down field and the right side is high field.
To define position of absorption, reference point used, TMS for both proton and C-13
NMR-a singlet peak. Chemical shift is referring to the exact place on the chart at which a
nucleus absorbs. The chemical shift of NMR absorption given in ppm or δ units is
constant, regardless of the operating frequency of the spectrometer.

The chemical shift for the reference (TMS) is 0ppm. The scale for the NMR chart
is 1 δ = 1ppm frequency spectrometer. So, if a spectrum 1H is getting from the instrument
operated at 60MHz, 1 δ is 1ppm from 60,000,00 or 60Hz. If we use the instrument
300MHz, so 1 δ = 300Hz.

δ = chemical shift (Hz from the TMS) x 106

Frequency spectrometer (Hz)

Chemical shift can reflect the structure of the molecule, so it can use to analysis
the structure of the unknown compound. Hydrogen is most abundant particle in many
organic compounds, so this method is widely used as we mention before. The strength for
the line in the spectrum is linear to the sum of the proton inside it. We can know the
distribution of the atom hydrogen in the organic molecule and get the relative
distribution. The chemical shift and the integral can give the information about the
number and types of hydrogen contained in a molecule. A third type of information to be
found in the NMR spectrum is that derived from the spin-spin splitting phenomenon. This
phenomenon can be explained by the n+1 rule.

The formula molecule for sample A is C 10H1203. The proposed structure for the
sample A is as below:

There are 2 readings for doublet peak, they are 7.336ppm and 7.302ppm. The H
proton bonded to the benzene ring give the reading of 6.974ppm. The reading for the
singlet peak is 3.861ppm, 3.775ppm and 2.6061ppm respectively.

The formula molecule for sample B is C 4H802. The proposed structure for the
sample B is as below:

The peak consist of a set of triplet peak at δ = 1.138,1.257 and 1.377ppm. As for the
singlet peak, that is at δ = 2.039ppm and for the quartet peak are at δ = 3.961, 4.078,
4.197 and 4.317ppm.

To get the more accurate result, we should take into consideration on the following
precaution steps:

• Use distilled water to rinse all the relevant apparatus.

• To get a more homogen solution, the sample should be rinse with the solvent.
• The NMR tube must be in the dry and clean condition.
• The NMR tube must handle with carefully because it is very expensive and
fragile.
• Make sure that the tube is placed vertically into the prob.
• Make sure that the height of the sample is ~35mm, if too little it cannot be
detected, and the result will become inaccurate if the sample is too much in the
tube.
• Use the suitable solvent to dissolve the sample completely.

Conclusion:
 1) The structure of sample A is

2) The structure of sample B is

3) The formula molecule for sample A is C10H1203.

4) The formula molecule for sample B is C4H802.
5) The spectrum of the sample A.

δ/ppm The data that we get

0.000 TMS
7.336 Doublet peak. There is 2-atom hydrogen, which are
7.302 neighbors to each other at one-C aromatic ring.
7.021 This is the peak for the solvent.
6.974 Singlet peak. There have no neighbors to the atom-H
at C-aromatic ring.
3.861 Singlet peak.
3.775
2.606

6) The spectrum of the sample B.

δ/ppm The data that we get

0.000 TMS
1.138 Triplet peak. There is a proton from CH3, which
1.257 possesses 2 neighbors.
1.377
2.039 The methyl group has no proton nearby singlet peak.
3.961 Quartet peak. The proton from CH2, which is
4.078 equivalent, gives one peak that gives 3-proton
4.197 neighbors.
4.317

References:
1) Introduction to Spectroscopy; 3rd edition, Donald L. Pavia, Gary M. Lapman,
George S. Kriz.
2) Laboratory Manual CHM3402 Spectroscopy, Chemistry Department Faculty Of
Science & Environmental Studies.
3) Analytical Chemistry, 5th edition,Gary D Christion.
4) Analytical Chemistry : An Introduction, 7th edition
D. A. Skoog, D. M. West, F. J. Holler, and S. R. Crouch