ABSTRACT

Nuclear Magnetic Resonance (NMR) spectroscopy is an analytical chemistry

technique used in quality control and research for the determining the content and
purify of a sample as well as its molecular structure (Hoffman, 2013). The main
objective for this experiment is to identify compounds of constitutional isomer using
the NMR analysis. There are 9 compounds which are A to I needed to be identical.
The data analysis of

13

C NMR and 1H NMR are given for each compound. The

constitutional isomers made up from three different species elements which are C, H
and O. Based on the percentage, the total molecular mass and relative atomic mass
of C, O and H we can get the value of compound that are made up to
1

the NMR data analysis of H NMR and

. From

13

C NMR, it can concluded that compound A

were Buta-1,2-dien-1-yl acetate, compound B were 2-methylcyclopentane-1,3-dione

,compound C were cyclohexane-1,4-dione , compound D were Ethenyl(2E)-but-2enoate ,compound E were Methyl-2-methyllidenbut-3-enoate , compound F were
Cyclobutylideneacetic acid , compound G were (3E)-5-hydrohexa-3, 5-dien-2-one,
compound H were 6-methyl-2, 3-dihydro-4h-pyran-4-one and lastly compound I were
Hex-2-ynoic acid.
INTRODUCTION

Nuclear Macnetic resonance (NMR) spectroscopy is an analytical chemistry

technique used in quality control and research for determining the content and purity
of

the

sample

as

well

as

its

molecular

structure(Chem).For

unknown

compounds,NMR can either be used to match against spectral libraries or to infer the
basic structure directly.Once the basic structure is known,NMR can be used to
determine molecular conformation in solution as well as studying physical properties
at

the

molecular

level

such

as

conformational

exchange,phase

changes,solubility,and diffussion.In order to achieved the desired results,a variety of

NMR techniques are available.
The principle behind NMR is have many nuclei that have spi 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.The energy transfer takes
place at a wavelength that corresponds to radio frequenciesand when the spins
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 and
NMR spectrum for the nucleus(Chem).

The frequency is gated,amplified and applied to the probe to generate an

excitation field.Frequency source is used to generate a wave at a frequency close to
the resonance frequency.Currently,NMR spectroscopy is being using in many field of
area such as in medicine,industries and also for research.This is becauce NMR
spectroscopy becomes a powerful analytical technology in order to determine the
physical and chemical properties of atom or molecule(molbiol).

THEORY
Nuclear Magnetic Resonance (NMR) spectroscopy is an analytical chemistry
technique used in quality control and research for the determining the content and
purify of a sample as well as its molecular structure (Hoffman, 2013). The theory
behind the NMR is that many nuclei have spin and all the nuclei have electrically
charged.
Nuclear Spin
Nuclear spin may be related to the nucleon composition of a nucleus in the following
manner:
i.

Odd mass nuclei whose those having an odd number of nucleons have a
fractional spins. For example, I = (such as 1H,13C,19F)

ii.

Even mass nuclei composed of odd numbers of protons and neutrons have
integral spins. For example, I = 1 (such as 2H,14N)

iii.

Even mass nuclei composed of even numbers of protons and neutrons have
zero spin. For example, I = 0 (such as 12C,16O)
Spin nuclei have a spherical charge distribution, and their NMR behavior is the

easiest to understand. Other spin nuclei have non-spherical charge distributions and
may be analyzed as prolate or oblate spinning bodies (Reusch, 2013). A spinning
charge generated a magnetic field. The figure 1 below showed that the case of the
spin nuclei.

Figure 1

Spin nuclei

(Source: http://chem.ch.huji.ac.il/nmr/whatisnmr/whatisnmr.html)
The resulting spin-magnet has a magnetic moment () proportional to the
spin. When the external magnetic field (B0) is present, two spin states exist which
are +1/2 and -1/2. The magnetic moment of the lower energy +1/2 spin state is
aligned with external field and the magnetic moment of the higher energy -1/2 spin
state is opposed to the external field. The arrow represents the external field points
North. Figure 2 show the structure of spin state.

Figure 2
(Source:

Spin state

http://chem-is-easy.blogspot.com/2013/01/characterisation-of-organic-

compounds_29.html)

The difference in energy between two spin states is dependent on the

external magnetic field strength and it is always very small. The two spin states have
the same energy when the external field is zero. Figure 3 shows the illustration for
the difference energy. It is diverge as the field is increases. At a field is equal to Bx, a
formula for the energy difference is given as shown below (Reusch, 2013).

Figure 3

Difference Energy

(Source:
http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/nmr/nmr1.htm)
Chemical Shift
An NMR spectrum is a plot of the radio frequency applied against absorption.
A signal in the spectrum is referred to as a resonance. The chemical shift is the
frequency of the resonance expressed with the reference to a standard compound
which is defined to be at 0 ppm. The reference compound is tetramethylsilane
(Si(CH3)4 which is also known as TMS. The scale is made more manageable by
expressing it in parts per million (ppm) and it is independent of the spectrometer
frequency. The equation below used to calculate the chemical shift.

When a peak at chemical shift, is between 5 ppm to 10 ppm, it is known as

deshielded or downfiled while a peak at chemical shift, is between 0 ppm to 5 ppm,
it is known as shielded or upfield. Figure 4 shows the scale of chemical shift.

Figure 4

Chemical Shift Scale

(Source: http://www.mhhe.com/physsci/chemistry/carey/student/olc/ch13nmr.html)

Shielding in H-NMR
The magnetic field experienced by a proton which is influenced by various
structural factors. Since the magnetic field strength showed the energy separation of
the spin states and hence the radio frequency of the resonance, the structural factors
mean that different types of proton will occur at different chemical shift. The
structural factors are inductive effects by electronegative groups and magnetic
anisotropy.
For electronegativity, the electrons around the proton create a magnetic field
that opposes the applied filed. Since this reduces the field experienced at the
nucleus, the electrons is said to shield the proton. When there are more
electronegative groups present, it will produce peak at deshielded area. The
chemical shifts for more electronegative groups become larger.
Magnetic anisotropy is that there is a non-uniform magnetic field. Electrons
in the systems interact with the applied field which induced a magnetic field that
causes the anisotropy. As a result, the nearby proton will experience three fields
which are the applied field, the shielding field of the valance electrons and the field
due to the system.

H-NMR Chemical Shifts

The chemical shift s the position on the scale in ppm where the peak is
occurs. There are two majors factors that influence the chemical shifts which are
deshielding due to reduced electron density (due electronegative atoms) and
anisotropy which due to magnetic field generated by bond. Figure 5 shows the HNMR chemical shift scale.

Figure 5

H-NMR Chemical Shift Scale

(Source:
http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/nmr/nmr1.htm)

Coupling in H-NMR
The spin-spin interaction of neighboring hydrogens takes place through the
covalent bonds that join them. The most common bonding relationship is vinical that
joined by three sigma bonds. In the case, a neighboring proton having a +1/2 spin
shifts the resonance frequency of the proton that being observed to a slightly higher
value and a-1/2 neighboring spin shifts to a lower frequency.
The statistical distribution of spins within each set explains the both n+1 rule
and the relative intensities of the lines within a splitting pattern. The action of a single
neighboring proton is easily deducted from the fact that it must have one of two
possible spins. Interaction of these two spin states with nuclei under an observation
leads to a doublet located at the expected chemical shift (Reusch, 2013). Figure 6
shows the multiplicity relative line intensity

Figure 6

Multiplicity Relative Line Intensity

(Source: http://www.mhhe.com/physsci/chemistry/carey/student/olc/ch13nmr.html)

C-NMR Spectroscopy
13

C has only 1.1% natural abundance (of carbon atoms).

12

C does not exhibit

NMR behavior which the nuclear spin, I=0. As a result, C is about 400 times less
sensitive than H nucleus to the NMR phenomena. Because of the low abundance,
the

13

C-13C coupling is usually not seeing in the NMR. The chemical shift range for

C-NMR is normally 0 to 220 ppm. The number of peaks indicates the number of
types of C. overlap of peaks is much less common than for H-NMR which makes it
easier to determine how many types of C are present. Figure 7 shows the chemical
shift for 13C scale.

Figure 7

13

C Chemical Shift Scale

(Source:
http://www.mhhe.com/physsci/chemistry/carey/student/olc/ch13nmr.html)

PROCEDURE
1. The sample was prepared and placed in a container to be used for the
experiment.
2. Sign in into the work station.Then the Topspin software was selected for the
experiment.
3. The sample that was prepared earlier was inserted into the NMR tube.
4. The NMR tube containing the sample that was connected with the
spinner,which was later inserted to the sample depth gauge.The central line
on the sample depth gauge should be in the middle of the sample depth
gauge.The central line on the sample gauge should be in the middle of the
samples depth.
5. Then,the black cap on top of the magnetic bore was removed.
6. The LIFT button was pressed.At the same time,the sample depth gauge was
removed.
7. To lock on a specific substance,select the lock display window and select the
substance to lock from the solvent table window.
8. On instruments without the automatic tuning and matching,you have to
manually tune and match the sample by adjusting the screws.
9. Go through the NMR process and get the result.

Figure 5.1

RESULT
COMPOUND
COMPOUND A

COMPOUND B

COMPOUND C

COMPOUND D

COMPOUND E

COMPOUND F

COMPOUND G

COMPOUND H

COMPOUND I

NMR

ANALYSIS

NMR

205.6, 189.8, 103.5, 82.8, 16.9 and 16.3

NMR

5.4(1,s), 4.5(1,qrt), 2.2(3,s) and 1.4(3,d)

NMR

194.0, 111.6, 30.1 and 5.7

NMR

2.4(4,t), 2.2(1,qrt) and 1.5(3,d)

NMR

208.3 and 37.6

NMR

2.7(8,t)

NMR

163.2, 147.0, 141.3, 121.7, 97.4 and 18.2

NMR

7.4(1,t), 7.1(1,qnt), 5.9(1,d), 4.7(2,d) and 1.9(3,d)

NMR

164.3, 141.5, 135.5, 127.2, 97.8 and 18.2

NMR

7.3(1,t), 6.0(2,s), 4.7(2,d) and 2.0(3,s)

NMR

193.0, 104.3, 70.0, 32.3 and 21.1

NMR

11.3(1,s), 5.5(1,s), 2.5(2,t), 2.4(2,t) and 2.0(2,qnt)

NMR

152.6, 152.1, 108.6, 106.3, 57.1 and 13.5

NMR

6.1(1,d), 5.9(1,d), 4.5(2,s), 2.3(1,s) and 2.3(3,s)

NMR

203.8, 149.9, 145.9, 32.1, 27.3 and 14.4

NMR

6.7(1,s), 2.4(2,t), 2.3(2,t) and 2.0(3,s)

NMR

158.5, 92.6, 72.9, 21.0, 20.7 and 13.4

NMR

9.7(1,s), 2.3(2,t), 1.6(2,sxt) and 1.0(3,t)

DISCUSSION
The main objective of this experiment is to identify compounds of constitutional isomer using
NMR analysis. There are 9 compounds A to I needed to be identified. The compound is
constitutional isomers. The data analysis from
NMR and
NMR are given for

each compound. The constitutional isomers are made up from three different species
element (C, O, and H). It is given the compounds having the following elemental
composition:
C= 64.3%
O=28.6%
H=7.2%
And relative mass of 112.1 g/mol.
Calculated the molecular weight of each element:
M

= 112.1 x 64.3% = 72.08 g/mol

= 112.1 x 28.6% = 32.06 g/mol

= 112.1 x 7.2% = 8.07 g/mol

It is known that the relative atomic mass for:

C=12.01 g/mol, O= 16 g/mol and H= 1.01 g/mol
=

= 6C

= 2O

= 8H

From calculation above, we can get ratio of the compound or the chemical compound to
compose of
. In identifying the structure of the compounds, graph of
NMR

chemical shifts and

NMR chemical shifts are used to determine and justified the
structure constructed. The results are :
Compound A:
NMR
205.6
189.8
103.5
82.8
16.9
16.3

NMR
Description
Ketone
Double bond
Double bond
Double bond
Sat.alkane
Sat.alkane

5.4(1,s)
4.5(1,qrt)
2.2(3,s)
1.4(3,d)

Description
Ester
Double bond
Sat.alkane
Sat.alkane

Name of the compound = Buta-1, 2-dien-1-yl acetate

Compound B:
NMR
194.0
111.6
30.1
5.7

NMR
Description
Ketone
Sat.alkane
Sat.alkane
Sat.alkane

2.4(4,t),
2.2(1,qrt)
1.5(3,d)

Description
Sat.alkane
Sat.alkane
Sat.alkane

Name of the compound = 2-methylcyclopentane-1, 3-Dione

Compound C:
NMR
208.3
37.6

NMR
Description
Ketone
Sat.alkane

2.7(8,t)

Name of the compound= cyclohexane-1, 4-dione

Description
Sat.alkane

Compound D:
NMR
163.2
147.0
141.3
121.7
97.4
18.2

NMR
Description
Ester
Double bond
Double bond
Double bond
Double bond
Sat.alkane

7.4(1,t)
7.1(1,qnt)
5.9(1,d)
4.7(2,d)
1.9(3,d)

Description
Double bond
Double bond
Double bond
Double bond
Sat.alkane

Name of the compound = Ethenyl (2E)-but-2-enoate

Compound E:
NMR
164.3
141.5
135.5
127.2
97.8
18.2

NMR
Description
Ester
Double bond
Double bond
Double bond
Double bond
Sat.alkane

7.3(1,t)
6.0(2,s)
4.7(2,d)
2.0(3,s)

Description
Double bond
Double bond
Double bond
Sat.alkane

Name of the compound = Methyl-2-methyllidenbut-3-enoate

Compound F:
NMR
193.0
104.3
70.0
32.3
21.1

NMR
Description
Carboxylic acid
Double bond
Double bond
Sat.alkane
Sat.alkane

11.3(1,s)
5.5(1,s)
2.5(2,t)
2.4(2,t)
2.0(2,qnt)

Description
Carboxylic acid
Double bond
Sat.alkane
Sat.alkane
Sat.alkane

Name of the compound =Cyclobutylideneacetic acid

Compound G:
NMR
152.6
152.1
108.6
106.3

57.1
13.5

NMR
Description
Ketone
Double bond
Double bond
Double bond
C-OH
Sat.alkane

6.1(1,d)
5.9(1,d)
4.5(2,s)
2.3(1,s)

2.3(3,s)

Description
Double bond
Double bond
Double bond
ROH
Double bond

Name of this compound = (3E)-5-hydrohexa-3, 5-dien-2-one.

Compound H:
NMR
203.8
149.5
145.9
32.1
27.3
14.4

NMR
Description
Ketone
Double bond
Double bond
Sat.alkane
Sat.alkane
Sat.alkane

6.7(1,s)
2.4(2,t)
2.3(2,t)
2.0(3,s)

Description
Double bond
Sat.alkane
Sat.alkane
Sat.alkane

Name of the compound = 6-methyl-2, 3-dihydro-4h-pyran-4-one

Compound I:
NMR

NMR
Description
Carboxylic acid
Triple bond
Triple bond
Sat.alkane
Sat.alkane
Sat.alkane

158.5
92.6
72.9
21.0
20.7
13.4

Description
Carboxylic acid
Sat.alkane
Sat.alkane
Sat.alkane

9.7(1,s)
2.3(2,t)
1.6(2,sxt)
1.0(3,t)

Name of the compound = Hex-2-ynoic acid

CONCLUSION
From the percentage, the total molecular mass and relative atomic mass of C,O and H we
can get the value of compound that are made up to

NMR and
acetate,

compound

. From the NMR data analysis of

NMR, it can concluded that compound A were Buta-1,2-dien-1-yl

B

were

2-methylcyclopentane-1,3-dione

,compound

were

cyclohexane-1,4-dione , compound D were Ethenyl(2E)-but-2-enoate ,compound E were

Methyl-2-methyllidenbut-3-enoate , compound F were Cyclobutylideneacetic acid ,
compound G were
(3E)-5-hydrohexa-3, 5-dien-2-one, compound H were 6-methyl-2, 3-dihydro-4h-pyran-4-one
and lastly compound I were Hex-2-ynoic acid.

Reference
Hoffman, R. (2013, March 19). Uses of NMR Spectroscopy . Retrieved from What is
NMR?: http://chem.ch.huji.ac.il/nmr/whatisnmr/whatisnmr.html
Nuclear Magnetic Resonance (NMR) Spectroscopy. (n.d.). Retrieved from
Spectroscopy:
http://www.mhhe.com/physsci/chemistry/carey/student/olc/ch13nmr.html
Nuclear Magnetic Resonance Spectroscopy . (2013, January 28). Retrieved from
Chemistry Blog: http://chem-is-easy.blogspot.com/2013/01/characterisationof-organic-compounds_29.html
Reusch, W. (2013, May 5). Nuclear Magnetic Resonance Spectroscopy. Retrieved
from
http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/nmr/nmr1.
htm