ABSTRACT The experiment is carried out in order to identify various compounds using the knowledge of UV-Vis and IR spectroscopy.

The experiment is carried out by obtaining and observing the IR spectrum by using UV-Vis and FTIR spectroscopy. By using the data obtained from the spectroscopy, the various compounds can be identified. The results indicates that compound A is ethanol, compound C is ethanoic acid, compound D is ethyl ethanoate, compound I is benzoic acid, compound J is bromoethane and compound K is ethane. The experiment is successful as all the compounds are indentified.

INTRODUCTION Ultraviolet Visible Spectroscopy (UV-Vis) Accordings to Skoog (5th Edition, Principles of Instrumental Analysis), absorption measurements based upon ultraviolet and visible radiation find widespread application for the quantitative determination of a large variety of inorganic and organic species. Molecular absorption spectroscopy is based on the measurement of the transmittance T or the absorbance A of solutions contained in transparent cells having a path length of b cm. Ordinarily, the concentration c of an absorbing analyte is linearly related to absorbance as represented by the Beer Lamberts equation. A = -logT = log = bc

The absorption of ultraviolet or visible radiation by an atomic or molecular species M can be considered to be a two-step process, the first of which involves electronic excitation as shown by the equation. M + hv M*

The product of the reaction between M and the photon hv is an electronically excited species symbolized by M*. The lifetime of the excited species is brief ( s), its existence

being terminated by any of several relaxation processes. The most common type of relaxation involves conversion of the excitation energy to heat; that is, M* M + heat
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Relaxation may also occur by decomposition of M* to form new species; such a process is called a photochemical reaction. Alternatively, relaxation may involve reemission of fluorescence or phosphorescence. It is important to note that the lifetime of M* is usually is so very short that its concentration at any instant is ordinarily negligible. Furthermore, the amount of thermal energy evolved by relaxation is usually not detectable. Thus, absorption measurements create a minimal disturbance of the system under study except when photochemical decomposition occurs. The absorption of ultraviolet or visible radiation generally results from excitation of bonding electrons; as a consequence, the wavelengths of absorption peaks can be correlated with the types of bonds in the species under study. Molecular absorption spectroscopy is, therefore, valuable for identifying functional groups in a molecule. More important, however, are the applications of ultraviolet and visible absorption spectroscopy to the quantitative determination of compounds containing absorbing groups.

Figure 1: Beers Law Absorption Law

Fourier Transform Infrared Spectroscopy (FT-IR) According to Skoog (5th Edition, Principles of Instrumental Analysis), the infrared region of the spectrum encompasses radiation with wavenumbers ranging from about 12,800 to 10 or wavelengths from 0.78 to 1000 . From the standpoint of both application and

instrumentation, the infrared spectrum is conveniently divided into near-, mid-, and farinfrared radiation; rough limits of each are shown in Table 16-1.
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The techniques and the applications of methods based upon the three infrared spectral regions differ considerably. Measurements in the near-infrared region are made with photometers and spectrophotometers similar in design and components to the instruments described in earlier chapters for ultraviolet/visible spectrometry. The most important applications of this spectral region have been to the quantitative analysis of industrial and agricultural materials and for process control.

TABLE 1: Infrared Spectral Region

Infrared absorption, emission, and reflection spectra for molecular species can be rationalized by assuming that all arise from various changes in energy brought about by transitions of molecules from one vibrational or rotational energy state to another. Most modern instruments utilize a dedicated microcomputer with versatile software capable of producing a variety of other output formats, such as transmittance versus wavelength and absorbance versus wavenumber or wavelength. A linear wavenumber scale is usually preferred in infrared spectroscopy because of the direct proportionality between this quantity and both energy and frequency. The frequency of the absorbed radiation is, in turn, the molecular vibrational frequency actually responsible for the absorption process. Basically, the Interferometer consists of a beam splitter, a fixed mirror, and a mirror that translates back and forth, very precisely. The beam splitter is made of a special material that transmits half of the radiation striking it and reflects the other half. Radiation from the source strikes the beam splitter and separates into two beams. One beam is transmitted through the beam splitter to the fixed mirror and the second is reflected off the beam splitter to the moving mirror. When reflected back by the mirrors, two beams of light recombine with each other at the beam splitter.

After the light is reflected from the two mirrors and back to the beam splitter, the original light will passes into the sample compartment. At there, the light is focused on the sample. On leaving the sample compartment the light is refocused into the detector. The difference in optical path length between the two arms to the interferometer is known as the retardation. An interferogram is obtained by varying the retardation and recording the signal from the detector for various values of the retardation. There is an interference occur between the two beams after they recombines. The interference creates variations in the output beam intensity as the difference in the path length changes. The intensity variations of the output beam can be measured with a detector as a function of the path difference. The intensity of each beam depends on the difference of path lengths in the two arms of the interferometer due to the effect of interference. The variation in the intensity of the beams seen by the detector as a function of the path difference, and a graph of this intensity can be plotted. The graph is known as interferogram. The data directly acquired by the FTIR instrument is in the form of an interferogram of the infrared light that passed through the sample. However, by just looking at the interferogram would not give any understanding of the sample characteristics. To get a normal spectrum with the wavelength along the horizontal axis, it requires a Fourier transform by the computer. This is the major characteristic of the FTIR instrument that differentiates it from a dispersive spectrophotometer, which measures spectra directly. If the distances travelled by two beams are the same, it means that the distance between two mirrors and the beamsplitter are the same. Thus, the situation is defined as zero path difference (ZPD). But, if the movable mirror moves away from the beamsplitter, the light beam which strikes the movable mirror will travel a longer distance than the light beam which strikes the stationary mirror. The distance which the movable mirror is away from the ZPD is defined as the mirror displacement and is represented by . It is obvious that the extra distance travelled by the light which strikes the movable mirror is 2. The extra distance is defined as the optical path difference (OPD) and is represented by delta. Therefore, =2

It is well established that when OPD is the multiples of the wavelength, constructive interference occurs because crests overlap with crests, troughs with troughs. As a result, a maximum intensity signal is observed by the detector. This situation can be described by the following equation: =n (n = 0,1,2,3...)

In contrast, when OPD is the half wavelength or half wavelength add multiples of wavelengths, destructive interference occurs because crests overlap with troughs. Consequently, a minimum intensity signal can be observed by the detector, and this situation can be described by the following equation: =(n+12) (n = 0,1,2,3...)

These two situations are two extreme situations. If the OPD is neither n-fold wavelengths nor (n+1/2)-fold wavelengths, the interference should be between constructive and destructive. So, the intensity of the signal should be between maximum and minimum. Since the mirror moves back and forth, the intensity of the signal increases and decreases which gives rise to a cosine wave. The plot is defined as an interferogram. When detecting the radiation of a broad band source rather than a single-wavelength source, a peak at ZPD is found in the interferogram. At the other distance scanned, the signal decays quickly since the mirror moves back and forth.

Figure 2: The Block diagram of an FTIR spectrometer

OBJECTIVES To identify the organic compounds by using UV-Vis. To identify the Organic Compounds by using FTIR.

THEORY UV-Vis Theory Absorbing species containing , , and n electrons include organic molecules and ions as well as a number of inorganic anions. Our discussion will deal largely with the former, although brief mention will be made of absorption by certain inorganic systems as well. All organic compounds are capable of absorbing electromagnetic radiation because all contain valence electrons that can be excited to higher energy levels. The excitation energies associated with electrons forming most single bonds are sufficiently high that absorption by them is restricted to the so-called vacuum ultraviolet region ( < 185 nm), where components of the atmosphere also absorb strongly. The experimental difficulties associated with the vacuum ultraviolet are significant; as a result, most spectrophotometric investigations of organic compounds have involved the wavelength region greater than 185 nm. Absorption of longer-wavelength ultraviolet and visible radiation is restricted to a limited number of functional groups with relatively low excitation energies. * Transitions. Here, an electron in a bonding orbital of a molecule is excited to the corresponding antibonding orbital by the absorption of radiation. The molecule is then described as being in the , * excited state. Relative to other possible transitions, the energy required to induce a * transition is large, corresponding to radiant frequencies in the vacuum ultraviolet region. Methane, for example, which contains only single CH bonds and thus undergo only * transitions, exhibits an absorption maximum at 125 nm. Ethane has an absorption peak at 135 nm, which must also arise from the same type of transition, but here electrons of the CC bond appear to be involved. Because the strength of the CC bond is less than that of the CH bond, less energy is required for excitation; thus, the absorption peak occurs at a longer wavelength. n * Transitions. Saturated compounds containing atoms with unshared electron pairs (nonbonding electrons) are capable of n * transitions. In general, these transitions require less energy than the * type and can be brought about by radiation in the region of between 150 and 250 nm, with most absorption peaks appearing below 200 nm. The energy requirements for such transitions depend primarily upon the kind of bond and to a lesser extent upon the structure of the molecule. The molar absorptivities associated with this type of absorption are low to intermediate in magnitude and usually range between 100 and 3000
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. Absorption maxima for the n * transition tend to shift to shorter

wavelengths in the presence of polar solvents such as water or ethanol. The number of organic functional groups with n * peaks in the readily accessible ultraviolet region is relatively small. n * and * Transitions. Most applications of absorption spectroscopy to organic compounds are based upon transitions for n to electrons to the * excited state because the energies required for these processes bring the absorption peaks into an experimentally convenient spectral region (200 to 700 nm). Both transitions require the presence of an unsaturated functional group to provide the orbitals. Strictly speaking, it is to these unsaturated absorbing centers that the term chromophore applies. The molar absorptivities for peaks associated with excitation to the n, * state are generally low and ordinarily range from 10 to 100 L ; values for * transitions, on the other hand, normally fall in

the range between 1000 and 10,000. Another characteristic difference between the two types of absorption is the effect exerted by the solvent on the wavelengths of the peaks. Peaks associated with n * transitions are generally shifted to shorter wavelengths with increasing polarity of the solvent.

Figure 3: Electronic Molecular Energy Levels

FT-IR Theory Absorption of infrared radiation is confined largely to molecular species that have small energy differences between various vibrational and rotational states. In order to absorb infrared radiation, a molecule must undergo a net change in dipole moment as a consequence of its vibrational or rotational motion. Only under these circumstances can the alternating electrical field of the radiation interact with the molecule and cause changes in the amplitude of one of its motions. For example, the charge distribution around a molecule such as hydrogen chloride is not symmetric because the chlorine has a higher electron density than the hydrogen. Thus, hydrogen chloride has a significant dipole moment and is said to be polar. The dipole moment is determined by the magnitude of the charge difference and the distance between the two centers of charge. As a hydrogen chloride molecule vibrates, a regular fluctuation in dipole moment occurs, and a field is established that can interact with the electrical field associated with radiation. If the frequency of the radiation exactly matches a natural vibrational frequency of a molecule, a net transfer of energy takes place that results in a change in the amplitude of the molecular vibration; absorption of the radiation is the consequence. Similarly, the rotation of asymmetric molecules around their centers of mass results in a periodic dipole fluctuation that can interact with radiation. No net change in dipole moment occurs during the vibration or rotation of homonuclear species such as , , ; consequently, such compounds cannot absorb in the infrared.

With the exception of a few compounds of this type, all other molecular species absorb infrared radiation. The energy required to cause a change in rotational level is minute and corresponds to radiation of 100 or less. Because rotational levels are quantized, absorption by gases in

the far-infrared region is characterized by discrete, well-defined lines. In liquids or solids, intramolecular collisions and interactions cause broadening of the lines into a continuum. Vibrational energy levels are also quantized, and for most molecules the energy differences between quantum states correspond to the mid-infrared region. The infrared spectrum of a gas usually consists of a series of closely spaced lines, because there are several rotational energy
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states for each vibrational state. On the other hand, rotation is highly restricted in liquids and solids; in such samples, discrete vibrational/rotational lines disappear, leaving only somewhat broadened vibrational peaks. The relative positions of atom in a molecule are not exactly fixed but instead fluctuate continuously as a consequence of a multitude of different types of vibrations and rotations about the bonds in the molecule. For a simple diatomic or triatomic molecule, it is easy to define the number and nature of such vibrations and relate these to energies of absorption. An analysis of this kind becomes difficult if not impossible for molecules made up of several atoms. Not only do large molecules have a large number of vibrating centers, but also interactions among several centers can occur and must be taken into account.

PROCEDURE For UV-Vis: A. TO TURN ON EQUIPMENT 1. The instrument is turned on. 2. The software PERKIN ELMER UV VISIBLE is turned on. 3. Click on New and click Method. 4. The type of instrument (HIGH PERFORMANCE UV/VIS/NIR) is selected and click on Next and the lambda for the instrument was chosen. 5. Click on Next and the method type is selected. 6. It is scanned and click Next (twice). 7. The name of method is saved and clicks OK.

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B. TO CREATE METHOD 8. Go to data collection. 9. The wavelength was set depending to manual lab. 10. Go to ordinate mode and the parameter (Absorption, transmittance, or reflection) was chosen. 11. Go to sample info and the sample is inserted. Then hit Enter. 12. The first sample is labelled as Blank. 13. The sample id is edited with the others sample (ex: Bromide 1, Bromide 2, and etc.) 14. The wavelength that we want to start was set like the way we set it before this. Then click Apply and OK. 15. Click button start. 16. Click OK. 17. Both are inserted with blank in the sample holder, and the clear windows are aligned with the optical path. 18. The blank at beam no 2 is removed and it is replaced with the other sample. Click OK. 19. Then, the spectrum is obtained. 20. The procedure no 11 is repeated until all sample finish.

C. TO SAVE DATA 21. Go to file, click to save as. 22. Click task and name of the file 23. After that, go to Processing, click Add, then the process that we want was selected (ex: Peak Table)
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24. Go to Report, click Template. The type of report that we want was chosen (ex: scan with Peak Table) then it was saved. 25. Go to the icon printer report and thick printer file. 26. The location to save the file is selected and it was saved.

For FT-IR: A. TO RUN SAMPLE 1. The computer is turned on. Click at software spectrum. 2. Click at background, and a pop-up Ready for scan sample is appeared on the screen. 3. Click at instrument scan. The box is appeared, and the information was key in. 4. Click at scan and the range to run sample is inserted. Start to end. 5. Click Apply and when the sample is ready, we started to scan. The top plate is cleaned with Acetone Liquid sample The sample is dropped into hole of top plate. Solid sample The sample is inserted into hole and it is purged. The sample is scanned. The top plate is cleaned again with acetone after used.

6. Click edit, and then copy (to copy the result into Microsoft Excel) 7. Click exit to log out from program.

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Result Reference solvent spectrum from UV-Vis spectroscopy:

0.010 0.005 0.000 -0.005 -0.010 -0.015 -0.020

-0.025 -0.030 -0.035 -0.040 -0.045 -0.050 -0.055 200 250 300 350 400

nm

Compound A : Ethanol IR-Spectra:

99.3

95

90

85

80
2880.20

1379.68

75
3330.00

631.93

70

2973.13

%T 65

60
1087.28

879.98

55

50

45

40

35 32.0 4000.0 3600 3200 2800 2400 2000 1800 cm-1 1600 1400 1200

1045.95

1000

800

600 515.0

UV-Vis spectra:
1.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 200 250 300 350 400

nm

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Compound C: Ethanoic Acid. IR spectra:

91.8 90

85

80
2629.37

75

1052.09

70
3035.36

65

1756.86

1012.48

60
888.71

55 %T 50
1407.59 605.89

45

626.63

40
1287.80

35

30

25
1704.74

20 16.0 4000.0 3600 3200 2800 2400 2000 1800 cm-1 1600 1400 1200 1000 800 600 515.0

UV-Vis spectra:
1.6 1.4 1.2 1.0

0.8 0.6 0.4 0.2 0.0 200 250 300 350 400

nm

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Compound D: Ethyl Ethanoate IR spectra:

100.2

95

90
786.15

85
1447.57 2984.79 938.16 1097.55 846.99

80

634.20

75
607.57

70

65

60 %T 55

50

1372.77

45

40

35

30
1043.56

25
1736.42 1233.66

20 16.0 4000.0 3600 3200 2800 2400 2000 1800 cm-1 1600 1400 1200 1000 800 600 515.0

UV-Vis spectra:
1.4 1.2 1.0 0.8

A
0.6 0.4 0.2 0.0 200 250 300 350 400

nm

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Compound I: Benzoic Acid IR spectra:

90.3

85
1789.99

80

1915.19

75

1496.46

3071.49

70
2874.27 2669.08 2945.49 2990.65 2829.18 2549.95

1100.72 1000.03

65

60
1601.11

1072.55 1026.55 1127.58

%T 55

1582.66 1179.57 804.19

50
1453.51 1419.82

45

40

1323.46

930.99 543.04 683.46

35
666.14

30
1678.82 1287.96 703.84

25 22.0 4000.0 3600 3200 2800 2400 2000 1800 cm-1 1600 1400 1200 1000 800 600 515.0

UV-Vis spectra:
4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 200 250 300 350 400

nm

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Compound J:Bromoethane IR spectra:

100.9 98 96 94 92
2866.85

90 88
2924.71

86
1377.05

84 82 80 78 76 74 %T 72 70 68 66 64 62 60 58 56 54 52 50 48 46 45.0 4000.0 3600 3200

2978.94

768.64

1442.38

958.76

1241.02 559.03

2800

2400

2000

1800 cm-1

1600

1400

1200

1000

800

600 515.0

UV-Vis spectra:
1.8 1.6 1.4 1.2 1.0

A
0.8 0.6 0.4 0.2 0.0 200

250

300

350

400

nm

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Compound K: Ethane IR spectra:

102.4 100

95

1753.53

90

935.05 971.51 845.59

582.49

85

1450.35

1043.89

80
2929.39

1350.59

75
1381.89

1252.77

1076.25

70

2860.77

%T 65

2976.76

60

55

50

45

40

35

1118.20

30.0 4000.0 3600 3200 2800 2400 2000 1800 cm-1 1600 1400 1200 1000 800 600 515.0

UV-Vis spectra:
1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 200 250 300 350 400

nm

DISCUSSION 18

Before proceeding to future explanations on the discussion chapter, some points will be described in order to answers some general question related to this experiment. First is why acetone is used as cleaning agent for FTIR. Acetone is a very good solvent which it is a very polar substance that dissolves almost all organic compounds, which is obviously the best cleaning agent. A common cleaning routine is to rinse with water first to wash away inorganic salts and then rinse with acetone to wash away the organic materials which the water cannot dissolve. Others, acetone is used because it is relative safe solvent which have much higher flashpoint that other alcoholic solvent such as methanol or ethanol. Acetone also inflammable compare to other alcoholic solvent. For UV-visible, the halogen beam deuterium used to produce different wave length. For this experiment, ethanol is used as reference solvent. The chemical property such as it is a good solvent leads to this selection. Other than that, ethanol is relative low cost. The reference sample is important because it provides the reference state for the UV-visible. The ethanol peak reading will not appear in the result eventhough it is presence in the sample. Thus, there must be some error occurs due to multiple usage of equipments and improper cleaning done by students. The obvious error is occurred on UV-visible due to old equipments. Next proceed to the sample analysis. Compound A is determined as Ethanol obviously from FTIR. From absorption band shown that it have functional groups O-H, C-CH3 C-O. From prediction, it showed the characteristics of ethanol. The spectra obtained from FTIR shows that there are wide broad band at 3330 cm-1.It shows the existence of OH (Hydroxyl) in the compound. There is also a peak located at 2973.13 cm-1. It shows the presence of C-H bond. From the spectra obtained by UV-Vis method, compound A shows absorption at around max= 220 nm. Next for compound C, the result is Ethanoic Acid. There are many peaks formed in the IR spectra. The peaks forming at 3035.36 cm-1 and 2629.37 cm-1 indicate the existence of C-H group. The peak at 1756.36 cm-1 in strong intensity, shows the existence of C=O group. The strong intensity around 3600 cm-1 indicates the presence of OH group. UV-Vis spectra shows that compound C absorbs at around max = 215 nm with intensity of 1.650. This indicates that there are bond systems in the compound and compound C is an ethanoic acid. For compound D, the absorption at 2984.79 cm-1 in the IR spectra refers to the CH group. The peak at 1736.42 cm-1 indicates the existence of C=O group. Absorption at the peak
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1043.56 cm-1 refers to C-O group. The UV-Vis spectra of compound D shows max = 214.11 nm with intensity of 1.425. Compound D is an ester, ethyl ethanoate. The IR spectra of compound I shows absorption at 2990.65 cm-1, indicating OH group. The peak at 1453.51 cm-1 indicates the existence of aromatic ring. The peak at 1678.82 cm-1 shows the existence of C=O group. The UV-Vis spectra show peaks at two different points. The first at max = 225 nm at intensity of 2.453 while the second peak is at max = 237 nm at intensity of 3.975. These peaks show the presence of benzene ring. Compound I can be identified as Benzoic acid. For compound J, the IR spectra show a peak at 559.03 cm-1 indicating a C-Br group. Thus, compound J is identified as an alkyl halide. Another peak exists at 2924.71 cm-1 that indicates C-H group. For compound K, the IR spectra show a peak at 2860.77 cm-1 which indicates C-H group. There is also another peak at 1118.20 cm-1 corresponding to C-O group. In the UV-Vis spectra for compound K, absorption occurs at max = 220 nm with intensity of 1.211. It may be due to the lone pair that exists in compound K. Compound K is Diethyl Ether.

CONCLUSION The experiment is carried out in order to identify various compounds using the knowledge of UV-Vis and IR spectroscopy. The experiment is carried out by obtaining and observing the IR spectrum by using UV-Vis and FTIR spectroscopy. By using the data obtained from the spectroscopy, the various compounds can be identified. The results indicates that compound A is ethanol, compound C is ethanoic acid, compound D is ethyl ethanoate, compound I is benzoic acid, compound J is bromoethane and compound K is ethane. The experiment is successful as all the compounds are indentified.

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REFERENCES D. A. Skoog, F. J. Holler, and T. A. Niemen, 1998, Principles of Instrumental Analysis 5th edition, United State of America: Brooks/Cole Thomson Learning. J. Clark, 2007, UV-Visible Absorption Spectra, retrieved from

http://www.chemguide.co.uk/analysis/uvvisible/theory.html Newport Corporation, 1996-2014, Introduction to FTIR Spectroscopy, retrieved from http://www.newport.com/Introduction-to-FTIRSpectroscopy/405840/1033/content.aspx

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