CH301: Applications and methods of instrumental analysis Lab report

Name: Richard B. MAKINI-PURCELL UNIVERSITY OF THE SOUTH PACIFIC, FIJI ID: s11053938 Lab group: B

Lab date: Monday 20th / 08 / 12

Due: Mon 27th/ 08 / 12

TITLE: QUALITATIVE ANALYSIS BY INFRARED SPECTROSCOPY (IRS)

ABSTRACT As samples subject to IR spectroscopy are either in solid or liquid forms different methods of sample preparation was undertaken. Solid sample preparations were carried out in two ways, one as mull and the other with a di (pellet). Liquid samples used sodium chloride disks/plates. Comparing IR spectra yielded, for Ketones lower absorption frequencies, and for aldehydes slightly higher. Absorption frequencies depend on various factors, namely aromaticity and conjugation, bulkiness of molecule and also electronegativity of species surrounding functional groups.

INTRODUCTION/PRINCIPLE Fourier transform infrared spectroscopy (FT-IR) is a technique which is used to obtain an infrared spectrum of absorption, emission, photoconductivity or Raman scattering of a solid, liquid or gas. The term Fourier transform infrared spectroscopy originates from the fact that a Fourier transform (a mathematical process) is required to convert the raw data into the actual spectrum.[1] This spectroscopy deals with the infrared region of the electromagnetic spectrum, that is light with a longer wavelength and lower frequency than visible light. As with all spectroscopic techniques, it can be used to identify and study chemicals.[2] In this lab exercise, FT-IR spectroscopy is to be undertaken, providing a hands on feel of the IR analysis technical details and equally important is to compare absorption frequency shifts of main functional groups and build a memory bank of the various frequency shifts. The absorptions measured in this exercise will be compared and correlated to typical absorption values showed in the pictorial given below in Figure 1. This shows the relative absorption ranges in wave numbers (1/cm), where wave numbers are proportional to frequency and energy.

Source: http://en.wikipedia.org/wiki/File:IR_summary_version_2.gif Infrared spectroscopy as a technique that provides insight to chemicals structures and allows studies to be done on chemical specie is an important tool in analytical fields not only in chemistry but in Biological areas, as well as in physics. AIM

To:

a) Obtain first hand experience in sample preparation

b) Compare carbonyl absorption frequencies of the various samples by FT-IR spectroscopy.

EXPERIMENTAL PROCEDURE This experiment was carried out in two parts, firstly the sample preparations, secondly the scanning of the samples using the Perkin Elmer Spectrum 100 FT-IR spectrometer. Before the samples were run, a background scan was carried out by the lab demonstrator. Sample preparation included solid and liquid sample types. In solid preparation, a tiny bit of sample and a majority of KBr powder (in the ratio 1:100) were grounded together using a mortar and pestle until the substance appeared very clear in appearance, then this was put into a di and mechanically pressed using a shifting spanner. Then the di was left alone to stand for a few minutes. Following this the di was placed gently in the sample area within the cavity box of the spectrometer and the scan run. Another solid sample preparation was with Nujol. This was grinded with the solid sample and sandwiched between the NaCl disks or plates. For the liquid samples, instead of a di, disks made of NaCl were used. These were carefully soiled with absolute ethanol and dried with Kim wipes (special wipes), making sure not to touch with bare finger tips, tips of sharp objects and also devoid of water, as these variables would introduce errors in the scan. A minute drop of liquid sample was placed on one of two disks, then the other placed on top the other. Air bubbles were made sure to be absent between the salt disks before inserting into the spectrometer. The IR spectrums were observed via PC using default software for the PerkinElmer Spectrum 100 FT-IR spectrometer.

RESULTS & ANALYSIS Shown below are the IR spectra constructed in Excel from the PerkinElmer Spectrum 100 FTIR spectrometer measurements. (Note that the spectrum from the instrument has the X- axis reversed in contrast to these Excel plots which have normal sequence starting with zero at the origin and increasing to the right) 1. Solids

45 40 35 30 Intensity 25 20 15 10 5 0 0 500 1000 1500

Caffeine

2000

2500

3000

3500

4000

4500

wave number (1/cm)

Fig. 1.0 (chemical structure source: http://en.wikipedia.org/wiki/File:Caffeine-2Dskeletal.svg)

45 40 35

Benzoic acid

30
Intensity 25 20 15 10 5 0 0 500 1000 1500 2000 2500 3000 3500 4000 4500 wave number (1/cm)

Fig. 1.1 (chemical structure source: http://en.wikipedia.org/wiki/File:Benzoes%C3%A4ure.svg ) 2. Ketones

Acetophenone
100 90 80 70 60 50 40 30 20 10 0 0 500 1000 1500 2000 2500 3000 wave number (1/cm) 3500 4000 4500

Fig. 2.0 (chemical structure source: http://en.wikipedia.org/wiki/File:Acetophenone_structure.svg )

Intensity

18 16 14 12 Intensity 10 8 6 4 2 0 0 500 1000

Benzophenone

1500

2000 2500 3000 wave number (1/cm)

3500

4000

4500

Fig. 2.1 (chemical structure source: http://en.wikipedia.org/wiki/File:Benzophenon.svg )

100 90 80 70 Intensity 60 50 40 30 20 10 0 0 500 1000

Cyclohexanone

1500

2000

2500

3000

3500

4000

4500

wave number (1/cm)

Fig. 2.2 (chemical structure source: http://en.wikipedia.org/wiki/File:Cyclohexanone.svg ) Table 1.0 Showing main bands and groups of bonds for Cyclohexanone 2946 (1/cm) 2922 (1/cm) 1719 (1/cm) 1452 (1/cm) Aromatic -CH ketone Carbonyl -CH2 species and -CH -C=O start of fingerprint region [1]

3. Aldehydes

90 80 70 60 Intensity 50 40 30

Cinnamaldehyde

20
10 0

500

1000

1500

2000

2500

3000

3500

4000

wave number (1/cm)

Fig. 3.0 (chemical structure source: http://en.wikipedia.org/wiki/File:Zimtaldehyd__cinnamaldehyde.svg )

Benzaldehyde
90 80 70 60 50 40 30 20 10 0 0 500 1000 1500 2000 2500 3000 3500 4000 4500

Intensity

wave number (1/cm)

Fig. 3.1 (chemical structure source: http://en.wikipedia.org/wiki/Benzaldehyde ) Table 2.0 Showing main bands and groups of bonds for Benzaldehyde 3090 (1/cm) 2831 (1/cm) 2748 (1/cm) 1709 (1/cm) 750 (1/cm) 675 (1/cm) Aromatic Aldehyde Aldehyde Aldehyde Aromatic Aromatic CH -CH -CH -C=O -CC -CC

n-butyraldehyde
90 80 70 60 50 40 30 20 10 0 0 500 1000 1500 2000 2500 3000 3500 4000 4500 wave number (1/cm)

Fig. 3.2 (chemical structure source: http://wtt-pro.nist.gov/wttpro/index.html?cmp=butanal )

INtensity

Table 3. Showing carbonyl frequencies for the different Aldehyde compounds Benzaldehyde Cinnamaldehyde n-butyraldehyde

1709 (1/cm)

1693 (1/cm)

1722 (1/cm)

Cinnamaldehyde spectrum obtained in this practical shows typical absorption frequency value for the carbonyl specie which was 1693 (1/cm), this lower range value satisfies the effect that a carbonyl next to a double bond or aromatic group should have. Whereas for benzaldehyde being a saturated compound, its frequency value is a bit shy of the typical value it should acquire about around 1730 (1/cm). Transversely, n-butyraldehyde having a carbonyl next to an aromatic ring should register around 1705 (1/cm) but experimentally has a higher value, overall in fact when compared with the other two compounds, at an absorption frequency of 1722 (1/cm) . Table 4. Showing carbonyl frequencies for ketones Acetophenone Benzophenone
Cyclohexanone

1689 (1/cm)

1657 (1/cm)

1719 (1/cm)

On commenting upon the three ketone compounds studied, Acetophenone satisfies the theoretical value of 1690 with a very close 1689 (1/cm) . This absorption value follows for species of carbonyls next to an aromatic ring and or double bond. As for benzophenone, the practical shows that its value has dropped in comparison to acetophenone and the prescription that it should have similar values to atephenone due to the aromatic rings attached to the carbonyl. Lastly, for Cyclohexanone its result was also typical for carbonyl specie on a six membered ring or acyclic ketone that it was measured at 1719 (1/cm) compared to typical result of 1715 (1/cm) DISCUSSION/QUESTIONS-ANSWERS 1. Make a comparison of the carbonyl frequencies of the ketones and aldehydes with regard to conjugation and aromatics. 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 such that overally, the carbonyl frequenciy 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 instruments software as too intense as one trough was intercepting the x-axis, providing doubt as to the credibility of the sample or the instruments 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 have resulted in lower absorption frequencies than for aldehydes. And that conjugation and aromaticity obviously adds to the decrease in frequency absorptions. 2. 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, 3factors 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 th 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. 3. 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 4. What are the main analytical applications of IR spectroscopy?

IR spectroscopy as a common analytical technique is used for many important applications, (adapted from Wikipedia website 2012)[3] to name a few: In monitoring applications. Where the amount of carbon dioxide gas concentrations in green houses and growth chambers are monitored over a long time period.

Analytical IR spectroscopy can be used in Forensic analysis for example, in polymer degradation and also in determining alcohol levels in the blood. Also in polymer manufacturing, IR spectroscopy is used to measure the degree of polymerization Aslo in semiconductor electronics where the field deals with chemical species, the utilization of IR spectroscopy has been successful.

5. Absorption of IR radiation by a molecule is quantized but the vibrational spectra appear as bands rather than as lines. Give a suitable explanation. Absorption of IR by a molecule does not show as a line but as a band despite quantization of vibrational energies, this may be explained as such, when a sample is subject to the IR scan, IR radiation is incident onto the sample and each different bond or group of bonds absorb the radiation at different rates depending on various factors. The obvious ones are aromaticity, position of double bonds, electronegativity of surrounding specie, the sizr and weight of atoms (bulkiness) etcThese factors affect the absorption of energy in such a way that we observe bands with peaks to dictate the energy level absorbed instead of fixed energy read outs that donot vary by a few wave numbers and intensity values when a IR scan is carried out. 6. Explain why water is not a suitable solvent for IR studies. Water as a solvent in IR is not be used because water absorbs strongly in the IR range, aswell as when used with the NaCl or KBr disks water can react with them and so will result in an inaccurate spectra when subject to IR scan.

CONCLUSIONS 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 the 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 aromaticity frequency shifts decrease. ACKNOWLEDGEMENT Acknowledgements are due to the authorities responsible for facilitating this course namely Culwick Togamana, and the lab demonstrator Ms. Rosalyn Lata. Lastly but not the least, I would

also like to thank my lab partners, for partaking fully in sharing responsibilities to result in the completion of the experiment in this session. REFERENCES 1. Griffiths, P.; de Hasseth, J.A. (18 May 2007). Fourier Transform Infrared Spectrometry (2nd ed.). Wiley-Blackwell. Viewed on 14th Aug. 2012. Retrieved from: http://en.wikipedia.org/wiki/Fourier_transform_infrared_spectroscopy 2. Wikipedia- The free encyclopedia. (2012). Infrared Spectroscopy. Viewed on 16th Aug. 2012. Retrieved from :http://en.wikipedia.org/wiki/Infrared_spectroscopy 3. Lau, W.S. (1999). Infrared characterization for microelectronics. World Scientific. Viewed on 14th Aug. 2012 Retrieved from: http://en.wikipedia.org/wiki/Infrared_spectroscopy#Uses_and_applications & BIBLIOGRAPHY 4. Zubrick J. W.(__) what-when-how In Depth Tutorials and Information, viewed on 9th Aug. 2012, Retrieved http://what-when-how.com/organic-chemistry-laboratory-survivalmanual/infrared-spectroscopy-part-1-laboratory-manual/ 5. IR Spectroscopy - http://www.youtube.com/watch?v=zpQGx4g3-lk&feature=related Uploaded by LuminolSynthesis on Dec 12, 2011 6. Infra-red Spectroscopy: Lecture. From 20to9.com http://www.youtube.com/watch?v=VsuIJmoOs6o&feature=related Uploaded by Franklychemistry on May 11, 2011 Presentation and Production: Frank Scullion Figures used 7. http://en.wikipedia.org/wiki/File:IR_summary_version_2.gif 8. http://wtt-pro.nist.gov/wtt-pro/index.html?cmp=butanal 9. : http://en.wikipedia.org/wiki/File:Caffeine-2D-skeletal.svg 10. http://en.wikipedia.org/wiki/File:Benzoes%C3%A4ure.svg ) 11. http://en.wikipedia.org/wiki/File:Acetophenone_structure.svg ) 12. : http://en.wikipedia.org/wiki/File:Benzophenon.svg 13. http://en.wikipedia.org/wiki/File:Cyclohexanone.svg 14. : http://en.wikipedia.org/wiki/File:Zimtaldehyd_-_cinnamaldehyde.svg 15. : http://en.wikipedia.org/wiki/Benzaldehyde 16. : http://wtt-pro.nist.gov/wtt-pro/index.html?cmp=butanal