CHM 3202

ORGANIC (II)
CHEMISTRY LAB REPORT
NAME: IZHHARUDDIN BIN SUIB
MATRIC NO:
190028
PARTNER & 1)HAMZAH BIN ABD AZIZ
MATRIC NO: 189391

EXP NO & TITLE: EXPERIMENT 1 :

INFRARED SPECTRA OF ALDEHYDES
SUBMISSION
AND KETONES
DATE:

DATE OF EXP:
22/2/2018
LECTURER: 1.Y.BHG. PROF.DR.GWENDOLINE EE
CHENG LIAN
2.DR. SITI MUNIRAH BINTI MOHD
FAUZI
DEMONSTRATOR: MARYAM AISYAH BINTI ABDULLAH
Experiment 1-CHM 3202
Title: Infrared Spectra of Aldehyde and Ketone

Objectives:

1.To make comparison of carbonyl absorption frequencies of selected aldehydes

and ketones.

2. To illustrate the effects of substituent and conjugation.

3. To study the assignments of the main absorptions for individual aldehyde and
ketone.

4. To analyze the spectra for band resulting from the C=O groups and explain the
absorptions.

Introduction:

First and foremost, infrared spectroscopy is the analysis of infrared light

interacting with a molecule. This can be analyzed in three ways by measuring
absorption, emission, and reflection. The main use of this method is in organic and
inorganic chemistry field. It was used by the chemist to determine the functional
groups in the molecules. IR spectroscopy measures the vibration of an atom and
based on the possible in order to determine the functional group. Generally,
stronger bonds and light atoms will vibrate at high stretching frequency (wave
number).
 Next, the identification of aldehyde and ketone is often required in the
laboratory equipments. Aldehyde and ketone exhibit a strong C=O bond
(stretching) in region from 1810 cm⁻¹. This is because the position is relatively
constant and the bond is of high intensity, it is easily recognized in infrared
spectra. The actual position of the C=O bond is affected by several factors, the
physical state, neighbor substituent ,conjugation, hydrogen bonding and ring strain.

Furthermore, aromatic aldehydes absorb at lower frequencies but for

aliphatic and aldehydes absorb in the region from 1740 to 1720 cm⁻¹.Aromatic
(aldehyde) absorb at lower frequencies because the internal hydrogen bonding also
absorb lower frequencies. The carbonyl group of ketones absorb at slightly lower
frequencies from that a corresponding aldehyde.

Lastly, a saturated aliphatic ketone has a carbonyl absorption frequency about

1415 cm⁻¹. Conjugation with a double bond causes absorption that shift to lower
frequency. Hydrogen attached to the carbon adjacent to the sp3 hybridized carbon
in aldehydes and ketones usually show up 2.0 until 2.5 ppm.
Result:

BENZALDEHYDE

FUNCTIONAL GROUP WAVE NUMBER, cm⁻¹

C=O 1703.00
C-H (ALIPHATIC) 2820.39 & 2738.80
C-H (AROMATIC) 3065.48
C=C 1654.61 & 1597.83
 CINNAMALDEHYDE

FUNCTIONAL GROUP WAVE NUMBER , cm⁻¹

C=O 1681.67
C-H (ALIPHATIC) 3336.11
C-H(AROMATIC) 1451.38
C=C (ALIPHATIC) 2243.91

n-BUTYRALDEHYDE

FUNCTIONAL GROUP WAVE NUMBER , cm⁻¹

C-H (ALIPHATIC) 2725.13
C=O 1727.56
 BENZOPHENONE

FUNCTIONAL GROUP WAVE NUMBER, , cm⁻¹

C-H (ALIPHATIC) 3055.16
C-H (AROMATIC) 1448.06
C=O 1652.03
C=C 2343.12

CYCLOHEXANONE

FUNCTIONAL GROUP WAVE NUMBER , cm⁻¹

C-H (ALIPHATIC) 2864.35
C=O 2940.12
 ACETOPHENONE

FUNCTIONAL GROUP WAVE NUMBER , cm⁻¹

C=O 1713.40
C-H stretch (AROMATIC) 2940.12
C=C 1685.65 & 1597.08
C-H bend (AROMATIC) 751.18
C-C KETONE 1222.86
Discussion :

Infrared spectroscopy is an analysis by observe the energy that released by

the atom. Basically, the atoms joined by covalent bonds that will undergo
molecular vibration. The bond will vibrate and produce energy in the waves
region. Generally, the energy will be absorb if the frequency of the radiation
matches the frequency of the vibration .The energy are been quantized when the
atom vibrate in infrared radiation. Only specific vibration energy levels are
allowed, depending on the functional groups. For example, the energy
corresponding to wave number 4000 to 400 cm⁻¹. The wavenumber start from the
highest value (4000 cm⁻¹) because cm⁻¹ is proportional to frequency and energy of
the molecule. Thus, it can be said that the reaction start from the moving atoms that
produce vibration energy that will be converted to the wave number (cm⁻¹).If the
spectrum is small and become packed ,it means that the region is undergoing
disturbance and noise.

Furthermore, there are two main type of vibration mode in infrared

spectroscopy which is stretching and bending. Carbonyl stretching bonding has
two types which is symmetrical and asymmetrical bonding. Asymmetrical
stretching band in acylic anhydride is more intense where as symmetrical
stretching band is more intense in cyclic anhydrides. By definition, stretching
involves rhythm displacement along the bond axis such as the interatomic distance
alternately increases and decreases. While, bonding involves a change in bond
angles between two bonds and an atom common to both . One important thing that
need to know is the vibration between homo nuclear diatomic molecules like
oxygen (O2), nitrogen (N2), and Br2 (bromine) do not produce a change in dipole
moment and hence these molecules do not give rise to an Infrared spectrum.

Apart from that, the carbonyl can shift at the spectrum analysis due to the
force which near to each other that make it become stronger .If the electron
delocalized , it will loss energy such as benzene .The bond length will decrease and
the force will change thus the peak been shifted. Next , an overtone band is the
spectral band that occurs in a vibrational spectrum of a molecule when the
molecule makes a transition from the ground state (v=0) to the second excited state
(v=2), where v is the vibrational quantum number that one gets after solving the
Schrödinger equation for the molecule under consideration. It takes only non-
negative integer values. Overtone is sometimes due to resonance such as Fermi
resonance which lead to two bands appearing close together when one is expected.
When an overtone or a combination band has same frequency or similar frequency
tofundamental , two bands appear and split at either side of the expected value and
are of equal intensity called Fermi doublet.

Halogenation is the replacement of one or more hydrogen atoms in an

organic compound by a halogen (fluorine, chlorine, bromine or iodine).As we
know, halogenated compound has strong absorption bands in the fingerprint and
aromatic regions. Thus , more halogen on the same Carbon results in an increase
in intensity and a shift to higher wave numbers. For example, the absorption due to
C-Cl bond and C-Br bond is below 800 1/cm.
 On benzaldehyde , between the region around 3000 cm⁻¹, there is C-H
aldehyde at wave number of 2820.39 cm⁻¹. The C=C of the bond is shown at
1654.61 cm⁻¹ prove that the presence of benzene.

On the spectrum of cyclohexane, the 2864.35 cm⁻¹ peak shows that C-H
presence at the stretching region. Plus, at the wave number of 1713.40 cm⁻¹ shows
that the presence of C=O structure at this compound at the stretching region which
also known as aliphatic ketone.

For the aldehyde ,the benzaldehyde ,cinnamaldehyde and n-butyraldehyde,

each of the compound have a different carbonyl frequency .The carbonyl
frequency for benzaldehyde is 1703.00 cm⁻¹.For cinnamaldehyde ,the carbonyl
frequency is 1681.67 cm⁻¹and the n-butyraldehyde is 1727.56 cm⁻¹.From the IR
value stated ,we know that the n-butyraldehyde have the highest value of carbonyl
frequency and followed by benzaldehyde and cinnamaldehyde. The reasons why n-
butyraldehyde have the highest frequency value is mainly because the structure of
the compound itself which is aliphatic that effect the force constant.

With regard to conjugation and aromatics, for the aldehydes,

cinnamaldehyde with a double bond coupled to an aromatic system presents a
rather bulky and or heavy species, the carbonyl frequencies measured was a lower
range value in comparison with the typical range for aldehyde carbonyls. But what
was not typical was the signal of this carbonyl in the practical, it was a very weak
trough or peak that was within the carbonyl range. This occurrence may be
associated with errors originating from the sample and or instrumental errors .This
particular spectrum was highlighted by the instrument’s software as too intense as
one trough was intercepting the x-axis, providing doubt as to the credibility of the
sample or the instrument’s scanning process itself. As for the other two aldehydes,
benzaldehyde despite being a saturated compound registered lower frequency than
n-butyraldehyde which should have received a lower frequency instead due to its
aromatic property and overall molecular size. Hence in this case, one may say that
errors must be associated.

The ketones results were typical and obeyed characteristic ranges in that
the most simple and smallest compound cyclohexanone, gave off the highest
frequency, followed by acetophenone with closely accurate frequency
measurement, and lastly benzophenone with the lowest frequency in the group.
Benzophenone can be said to be a heavy and bulky molecule, hence the vibrational
energies absorbed were small as larger energy was needed to sufficiently vibrate
and energize the compound to give higher absorption frequencies.

All in all, the ketone specie has resulted in lower absorption frequencies
than for aldehydes and that conjugation and aromaticity obviously adds to the
decrease in frequency absorptions.

There are precautions step need to be taken in the experiment. Firstly, we

need to do water treatment towards to the sample in order to remove all water in
the sample before running the spectrometer. Next, handle the salt plates with care
as it is very sensitive to the moisture and will break easily. When dealing with the
computer, keyboard and mouse, make sure to remove gloves to avoid
contamination. If the sample is too concentrate, separate the plates and wipe one
side clean before putting them back together. Make sure we have to do background
before running the sample. Precaution step is important because to avoid errors
such as noisy lines in the spectrum and big peak band.

There are many errors that can happen in this experiment such as random
errors due to incomplete separation and removal of water content in the sample that
lead to noisy lines in the spectrum. Next, the systematic error that comes from the
computer data system which sometime we forgot to utilize more to the x-axis and
y-axis component such as transmittance and wave number. Lastly, the human error
such as the spectrum shows a worse result of peak due to unwashed of the
spectrometer at the background.

Conclusion:

Upon completion of this lab exercise on FT-IR spectroscopy, one can

positively state that experience was gained on sample preparation using the
methods of mull preparation and KBr for solid samples and NaCl disks for liquid
samples. As well as the precautions affiliated with these sample preparations in
order to obtain credible results. On the other aspect, a memory bank consisting of
absorption frequency shifts for carbonyls as well as the compounds’ variables
affecting frequency shifts has been built. From the exercise one can note that with
conjugation and aromatic frequency shifts decrease

1. We had make comparison of carbonyl absorption frequencies of selected

aldehydes and ketones and illustrate the effect of substituent and conjugation.

2. We had made the assignments of main absorptions for individual aldehydes and
ketones.
3. The analysis of the spectra for bands resulting from the C=O groups and the
absorption’s explanation had been made.

References:

1. http://wtt-pro.nist.gov/wtt-pro/index.html?cmp=butanal

2.https://chem.libretexts.org/LibreTexts/Athabasca_University/Chemistry_360%3
A_Organic_Chemistry_II/Chapter_19%3A_Aldehydes_and_Ketones%3A_Nucleo
philic_Addition_Reactions/19.14_Spectroscopy_of_Aldehydes_and_Ketones

3. http://www.mendelset.com/articles/695/aldehydes_and_ketones

4. https://www.amherst.edu/system/files/media/1449/Exp11.pdf

5. https://instruct.uwo.ca/chemistry/283g/labs/Experiment%206/Experiment%206-
2007.pdf

6. C.N.
Banwell and E.M.McCash:Fundamentals of Molecular Spectroscopy, Tata
McGraw-Hill Fourth Edition
Questions:

1. Explain how a shift in the carbonyl frequency can occur also by replacement
of an alkyl group with a chlorine atom.

A shift in carbonyl frequency can occur as a result of various factors,

three factors one can think of , one would be the size or weight of the
surrounding atoms, secondly, the type of bonds in the surrounding area to the
carbonyl and lastly involvement of electronegative species in the compound.
These factors should vary the frequency either by an increase or a decrease.
Now for replacement of an alkyl by chlorine this would be categorized as
introducing an electronegative species into the mix, and so this should result in
an increased absorption frequency, as evident by the slightly higher frequencies
that can be observed from acid chlorides.

2. At what frequency would you expect the overtone for the C=O stretch
of acetophenone to occur?

The overtone of C=O stretch in acetophenone should be at around 3378 1/cm.